J Delgado-Gallardo1, G L Sullivan2, M Tokaryk1, J E Russell3, G R Davies4, K V Johns4, A P Hunter5, T M Watson2, S Sarp1. 1. SPEC, College of Engineering, Swansea University, Swansea SA2 8PP, U.K. 2. SPECIFIC, College of Engineering, Swansea University, Swansea SA2 8PP, U.K. 3. Advanced Imaging of Materials Facility, Bay Campus, College of Engineering, Swansea University, Swansea SA1 8EN, U.K. 4. Technical Development Center Analytical Laboratory, Tata Steel Europe, Harbourside Business Park, Port Talbot SA13 1SB, U.K. 5. National Mass Spectrometry Facility, Swansea University Medical School, Singleton Park, Swansea SA2 8PP, U.K.
Abstract
The COVID-19 pandemic has increased the worldwide production and use of disposable plastic face masks (DPFMs). The release of micro- and nanopollutants into the environment is one of the impacts derived from regulated and unregulated disposal of DPFMs. This study focuses on the emission of pollutants from medical-grade DPFMs when submerged in deionized water, simulating regulated and unregulated disposal of these masks. Three brands of FFP2 and three brands of Type IIR medical masks, produced in various countries (UK, EU, and non-EU), were investigated. Field emission gun scanning electron microscopy (FEG-SEM) was used to obtain high-resolution images of the micro- and nanoparticles, and 0.02 μm pore size inorganic membranes were used to retain and subsequently analyze smaller particle size nanoparticles (>20 nm) released from the DPFMs. Particles and fibers in the micro- and nanoscale were found in all six DPFM brands. SEM with energy-dispersive spectroscopy analysis revealed the presence of particles containing different heavy metals like lead, mercury, and arsenic. Inductively coupled plasma mass spectrometry analysis confirmed the leaching of trace heavy metals to water (antimony up to 2.41 μg/L and copper up to 4.68 μg/L). Liquid chromatography-mass spectrometry analysis identified polar organic species related to plastic additives and contaminants such as polyamide-66 monomers and oligomers.
The COVID-19 pandemic has increased the worldwide production and use of disposable plastic face masks (DPFMs). The release of micro- and nanopollutants into the environment is one of the impacts derived from regulated and unregulated disposal of DPFMs. This study focuses on the emission of pollutants from medical-grade DPFMs when submerged in deionized water, simulating regulated and unregulated disposal of these masks. Three brands of FFP2 and three brands of Type IIR medical masks, produced in various countries (UK, EU, and non-EU), were investigated. Field emission gun scanning electron microscopy (FEG-SEM) was used to obtain high-resolution images of the micro- and nanoparticles, and 0.02 μm pore size inorganic membranes were used to retain and subsequently analyze smaller particle size nanoparticles (>20 nm) released from the DPFMs. Particles and fibers in the micro- and nanoscale were found in all six DPFM brands. SEM with energy-dispersive spectroscopy analysis revealed the presence of particles containing different heavy metals like lead, mercury, and arsenic. Inductively coupled plasma mass spectrometry analysis confirmed the leaching of trace heavy metals to water (antimony up to 2.41 μg/L and copper up to 4.68 μg/L). Liquid chromatography-mass spectrometry analysis identified polar organic species related to plastic additives and contaminants such as polyamide-66 monomers and oligomers.
The
SARS-CoV-2 pandemic has increased the worldwide use of disposable
plastic face masks (DPFMs) to safeguard the population’s health.
The wearing of face coverings has been made mandatory in various settings
in an effort to protect the general population.[1] Because of the subsequent increase in demand, the production
rates for masks in the UK have been increased by setting up several
new, or improved, manufacturing facilities.[2,3] Similarly,
in Europe, the production capacity has increased 20-fold, compared
to prepandemic levels, to 1.5 billion masks a month.[4] This increment in face mask usage has led to a surge of
DPFMs entering the marine environment, contributing to greater pollution
of these bodies of water[5] in the form of
macro-, micro-, and nanoplastics (NPs).There are a variety
of types of disposable masks that differ based
on their use and classification under relevant standards. Two such
types designed for medical use are FFP2 and Type IIR, which are classified
as a respirator mask and as a surgical mask under the British Standards
BS EN 149:2001 + A1:2009 and BS EN 14683:2019, respectively. These
two types offer different forms of protection: FFP2 protects the wearer
from infection, while Type IIR is intended to protect the wearer’s
surroundings.[6] As they offer greater protection,
FFP2 masks are recommended for use within high-risk areas, such as
in hospitals,[7] while Type IIR masks, although
still used in medical applications, are the more common of the two
types used among the general population.[8] In addition, under normal circumstances, both designs of masks would
be required to obtain CE marking (approved to be sold in the European
Economic Area) before sale within the European Economic Area and the
UK to show that they are safe and legal.[9] However, to prevent delays in new products entering the market during
the pandemic, some products have been authorized for sale without
this assessment and markings.[10] Different
brands of masks of the same design may display different CE numbers
depending on which notification body is used for the assessment of
the masks.[11]Even when businesses
and organizations usually have a standard
procedure for the disposal of DPFMs, a great amount of them are disposed
incorrectly by the general public. DPFMs are potentially a source
of microplastics (MPs) and NPs as well as other secondary contaminants.[12] The secondary pollutants that may be released
are of particular concern as the compounds used can pose significant
risks to the environment.[13] Elements like
arsenic, lead, mercury, and antimony, among others were found as part
of the particles released into water by the DPFMs selected in this
study.MPs and NPs are formed, among others, after the degradation
of
single-use plastic products, like disposable face masks (referred
to as secondary MPs) by ultraviolet (UV) light or mechanical means.[14] In addition, there is also the potential for
particles to be released directly, without the need for material breakdown,
as research has shown that masks can have a significant amount of
loosely attached plastic particles.[15,16]Recent
studies have pointed at the contribution of DPFMs, via direct
disposal or by laundering, to the aquatic plastic pollution during
and beyond the pandemic.[17,18] This contamination
also extends to soil[19] and ultimately to
wildlife.[20] Research has shown that both
MPs and NPs can have toxic effects if they are ingested and can be
transferred along the food chains by ingestion and bioaccumulation
and have effects on the development and reproduction of the organisms
by interfering with their metabolism.[21] Furthermore, these particles can adsorb contaminants already present
in the water and transport them, if they are ingested, into marine
animals, leading to an increased build-up of harmful compounds within
the animals.[22] A recent study has also
investigated the risk of particle inhalation posed by wearing DPFMs.[23]Determining which plastics and other pollutants
are released from
these FFP2 and Type IIR masks when they are submerged in water can
then help establish the wider impact their use will have on the environment.
The current studies found on this topic used Fourier transform infrared
(FT-IR) spectroscopy to determine the plastics used within respirator
and/or surgical masks. These studies revealed plastics that are known
to form nanoparticles, but the research did not generate or analyze
any NPs or other contaminants released from the masks.[24−26]This study incorporates field emission gun-scanning electron
microscopy
(FEG-SEM) and uses 20 nm pore size inorganic membranes in order to
retain and analyze particles below 100 nm, which is widely accepted
as the boundary of the nanoscale. The nanoscale is defined between
1 and 100 nm,[27] and it marked the size
limit described by the authors of previous research.[16] The study focuses exclusively on medical DPFMs manufactured
in various countries (UK, EU, non-EU), including a Type IIR brand,
which was used by the UK National Health Service (NHS).Several
technologies, including SEM, inductively coupled plasma
mass spectrometry (ICP-MS), and liquid chromatography–mass
spectrometry (LC–MS), were used to detect and characterize
organic and inorganic pollutants. Some concerning heavy metals (i.e.,
mercury) previously undetected were identified along with a vast range
of other components.
Methodology
Leaching and Separation of Particles
For this study,
a selection of six different brands of DPFMs, three
FFP2 and three Type IIR (Figure ), from different manufacturers (Table ), were acquired from Amazon. The FFP2-type
masks used were sold under the brands Baltic, Soyes Geji (referred
to as Geji within this paper), and Soyes. While the Type IIR brands
were Omnitex, Duronic, and ones certified for use in COVID-19 test
centers, and other environments, by the NHS. All the masks used were
confirmed to conform to the relevant British Standard.
Figure 1
Images of masks used
for this investigation. (A) Omnitex (showed
as an example of all three Type IIR DPFMs), (B) Baltic (same features
as Soyes), and (C) Geji (both FFP2 type).
Table 1
Manufacturer and Distributor Information
for DPFMs Used in the Experiment
Images of masks used
for this investigation. (A) Omnitex (showed
as an example of all three Type IIR DPFMs), (B) Baltic (same features
as Soyes), and (C) Geji (both FFP2 type).For
each batch of experiments, three sets of three of the same
brand of mask were placed into beakers with 1 L of deionized water,
dispensed from a Milli Q type 1 dispenser. The masks were left submerged
for 4 h at room temperature with gentle agitation using a glass stirrer,
once an hour. The same procedure was repeated with a beaker containing
only deionized water to be used for blank/control tests.After
submersion, the leachate was filtered through either a 0.1
μm or a 0.02 μm Al2O3 Whatman Anodisc
membrane under vacuum using an Aldrich glass funnel and receiving
flask. Three repetitions were conducted using each membrane pore size
for each brand of DPFMs. Once all the leachate from a beaker had been
filtered, the membrane was placed within a glass Petri dish and allowed
to dry at room temperature overnight. Using a beaker containing only
deionized water, a blank membrane was also treated using the same
filtration method as described above.
Microscopy
of Leached Particles
Light
microscopy of the membranes was used to determine the coverage of
particle contamination, and this was done using a Zeiss Primotech
microscope (Carl Zeiss Ltd., Cambridge, UK) at 50× and 500 overall
magnification.For SEM and energy-dispersive X-ray spectroscopy
(EDX) analysis, a Tabletop Microscope TM3000 was utilized (Hitachi
High-Technologies Corporation), and samples were mounted on carbon
tape and placed in a vacuum chamber.A new technology was also
put in place. Furthermore, high-resolution
characterization was conducted using a secondary electron detector
on a JEOL 7800F field emission gun scanning electron microscope (JEOL,
Tokyo, Japan). Prior to imaging, these samples were coated in 10 nm
of platinum.
ICP-MS Elemental Analysis
for Heavy Metals
in Leachates
Three DPFMs from each brand (labeled; Baltic,
Duronic, Geji, NHS, Omnitex, and Soyes) were submerged in 250 mL of
deionized water and left for 24 h. The aqueous portion (50 mL) of
the previous sample solution, termed the “leachate,”
was then aliquoted into clean centrifuge tubes and acidified using
1 mL of 1 M nitric acid. The leachates were analyzed for metal impurities
using a Perkin Elmer ICP-MS NexIon 2000, a common method for elemental
analysis in aqueous samples. A procedural blank (deionized left in
glass container for 24 h) and reagent blank (deionized water only)
were run with samples to check for background interference. To ensure
there was no carryover, blanks were run after the highest calibration
and after every sample. Calibration curves for each heavy metal tested
can be found in the Supporting Information (Figures 46S–58S). QC10, LOD, and procedure blank analyses are
also supplied in the Supporting Information (Table 1S).A calibration standard, containing a mixture of
heavy metals (As, Cd, Cr, Co, Cu, Mo, Ni Pb, Sb, Ti, and Hg) was acidified
using 10% HNO3 and diluted to a calibration range of 1
to 20 μg/L. An external calibration curve was generated from
the injection of the diluted standards, and it required regression
statistics above 0.9990 to be deemed acceptable. The samples that
were concentrated above 20 μg/L were further diluted using acidified
(10%) deionized water to bring into the dynamic range of the method.
A number of quality control samples, prepared from a separate batch
of multielement standards and run at the midrange of the method (10
μg/L), were put in place to assess the accuracy and precision
of the analytical method, and they were required to be below 10% for
both to be deemed acceptable. The instrument parameters were optimized
prior to running samples and were set using the following conditions:
plasma gas flow set at 18 L/min of argon, auxiliary gas flow set at
1.8 L/min, and nebulizer flow rate set at 0.98 L/min. The sample uptake
was set at 300 μL/min with three replicates per sample. The
radio-frequency voltage was applied at 1600 W, as determined by method
optimization during method development.
LC–MS
Screen for Organic Compounds
in Leachates
As shown in Section , three DPFMs from each brand were placed
in 250 mL of deionized water and left for 24 h. The leachate was removed
and analyzed using reverse-phase high-pressure liquid chromatography
(HPLC), with positive electrospray mass spectrometry (ESI-MS). No
sample pretreatment was performed on the leachate. Five microliters
of the sample were loop-injected into the pretuned and calibrated
LC/MS system. The system blanks and procedural blanks were run to
identify the background ions and assess any potential carryover.Organic contaminants were identified using a Thermo LTQ Orbitrap
XL accurate mass spectrometer based on the empirical formula deduced
from the accurate mass calculations and isotope patterns. For chromatographic
separation, a reverse-phase XBridge C18 column, with dimensions 3.5
μm × 2.1 mm × 150 mm, and a Guard column: XBridge
C18, 3.5 μm × 2.1 mm × 10 mm, were used for analyte
separation, with a flow rate of 150 μL/min for LC/MS. The composition
of the mobile phase A was 0.1% formic acid; 2% (acetonitrile) MeCN
in (water) H2O, and the mobile phase B was 0.1% formic
acid in MeCN. The elution gradient started at 2% B and increased to
90% at 32 min before returning to 2% B and ending with a total run
time of 37 min.A Dionex Ultimate 3000 HPLC system was connected
in series to a
Thermo LTQ Orbitrap XL accurate mass spectrometer, with an API ion
spray source. The MS parameters were optimized for a typical screening
method. The following conditions were used: sheath gas flow was set
to 15 L/min, auxiliary gas flow was set at 2 L per minute, and the
probe voltage was set at 4.3 kV with a capillary and tube lens voltage
of 43 and 150 V, respectively. The MS scan conditions were full mass
profile mode m/z 200–1000
with a resolution of 60,000 and a mass error of 0.5 ppm.
Results and Discussion
Optical Microscopy of Membranes
Light
microscopy analysis revealed that all the masks tested emitted fibers
visible at 50× overall magnification. The colors of the fibers
seen were in line with the visual appearance of the masks they originated
from, namely, white and blue fibers from the Type IIR masks, white
from the Baltic and Geji masks, and black from the Soyes masks. Figure 1S (see the Supporting Information) and Figure below show the microscopy images for 0.1 and 0.02 pore size
membranes, respectively, for each of the brands and the blank sample
at 50× magnification. More images of the replicates can be found
in the Supporting Information (Figure 4S–31S). All three of the FFP2 masks emitted significantly greater amounts
of microplastic fibers and particles than all Type IIR masks. Optical
microscopy image counting of areas of 3 μm2 gave
four to six times higher particle amounts released from FFP2 masks
than Type IIR masks. This result contravenes the findings of previous
research on the inhalation of MPs in air which found that N95 masks,
which are approximately equivalent to FFP2 masks, emitted lower amounts
of fibers than Type IIR masks.[23] The difference
found in this work may be due to the fact that the fiber structure
of melt-blown fabrics, which make up the inner layers of both designs
of masks as stated in the information provided by the manufacturers,
is known to be damaged during washing with water.[23] As FFP2 masks have three inner layers,[28] compared to the single layer in Type IIR masks,[26] there is a larger amount of fabric to be damaged
in this design of mask, potentially leading to a greater number of
emitted fibers.
Figure 2
Light microscopy images at 50× overall magnification
of 0.02
μm pore size membranes for all brands after filtration. (A)
Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic, (E) NHS, (F)
Omnitex (all Type IIRR), and (G) blank.
Light microscopy images at 50× overall magnification
of 0.02
μm pore size membranes for all brands after filtration. (A)
Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic, (E) NHS, (F)
Omnitex (all Type IIRR), and (G) blank.In addition to the fibers, all the mask brands also emitted smaller
fragments that were retained by the membranes, some of which required
500× overall magnification. These particles ranged in size from
around 100 μm to approximately 1.5 μm, which aligns with
the size of microplastic particles (<1 mm).[29] The number of these fragments detected was limited for
all brands, except for the membranes used to filter the Geji mask
leachates. This can be seen in Figure 2S (see the Supporting Information) and Figure below, which shows
the microscopy images from both 0.1 and 0.02 pore size membranes,
respectively, taken at 500× magnification, for each brand and
the blank sample.
Figure 3
Light microscopy images at 500× overall magnification
of 0.02
μm pore size membranes for all brands after filtration. (A)
Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic, (E) NHS, (F)
Omnitex (all Type IIRR), and (G) blank.
Light microscopy images at 500× overall magnification
of 0.02
μm pore size membranes for all brands after filtration. (A)
Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic, (E) NHS, (F)
Omnitex (all Type IIRR), and (G) blank.As the number of fragments emitted from the other FFP2 masks was
similar to the amount released by the Type IIR masks, a large number
of fragments from the Geji masks were thought to be likely due to
the foam nose cushions, which were only present on this brand of mask.
Foams of this type in the microplastic form are known to have effects
on microbial ecosystems in marine sediment,[30] as well as leaching harmful additives.[31] As such, these fragments pose a similar risk to the environment
as the other fragments and fibers released by the masks; however,
some strains of bacteria and fungi have been reported as being able
to efficiently degrade the foams.[32]
Analysis of Micro- and Nanoparticles with
SEM
The images taken using SEM techniques show the deposition
of fibers and particles in all membranes. The particles with lighter
colors usually contain heavier elements. The difference between the
mask leachates and the blank membranes, which were filtered with deionized
water and left for 4 h and stirred, the same as the other samples,
is notable, as the number of particles is clearly much lower on the
blanks. Apart from that, the NHS brand was the one with a lower number
of particles on the surface (Figure ).
Figure 4
SEM images at ×400 for all 0.02 μm membrane
surfaces
after filtration. (A) Baltic, (B) Geji, (C) Soyes (all FFP2), (D)
Duronic, (E) NHS, (F) Omnitex (all Type IIRR), and (G) blank membranes
(only deionized water was filtered).
SEM images at ×400 for all 0.02 μm membrane
surfaces
after filtration. (A) Baltic, (B) Geji, (C) Soyes (all FFP2), (D)
Duronic, (E) NHS, (F) Omnitex (all Type IIRR), and (G) blank membranes
(only deionized water was filtered).This difference in the number of particles deposited between blank
membranes and the rest was confirmed by the second FEG-SEM. Figure 3S (see the Supporting Information) and Figure show results for 0.1 and 0.02 pore size membranes, respectively.
More images of the replicates can be found in the Supporting Information
(Figures 32S–45S).
Figure 5
FEG-SEM images of 0.02
μm pore size membranes for all brands
at ×5000. (A) Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic,
(E) NHS, (F) Omnitex (all Type IIRR), and (G) blank.
FEG-SEM images of 0.02
μm pore size membranes for all brands
at ×5000. (A) Baltic, (B) Geji, (C) Soyes (all FFP2), (D) Duronic,
(E) NHS, (F) Omnitex (all Type IIRR), and (G) blank.The presence of nanoparticles (>100 nm) was also confirmed
in all
brands (Figure ).
Figure 6
SEM images
of nanoparticles found on the membrane surfaces after
filtration. (A) Baltic, (B) Duronic, (C) Geji, (D) NHS, (E) Omnitex,
and (F) Soyes.
SEM images
of nanoparticles found on the membrane surfaces after
filtration. (A) Baltic, (B) Duronic, (C) Geji, (D) NHS, (E) Omnitex,
and (F) Soyes.
SEM with
Energy-Dispersive Spectroscopy Elemental
Characterization of Particles
The composition of the particles
and element traces found in all brands and blanks are detailed as
follows, and the presence of these traces is shown in Table . Traces of diverse elements
and heavy metals like antimony, arsenic, cadmium, chlorine, iron,
lead, mercury, nickel, platinum, silicon, tin, and titanium, among
others, were found in all brands of this study, to a greater or lesser
extent (Figures 59S–61S in the Supporting
Information). The sorption and subsequent desorption of metals and
metalloid cations by MPs have been proven, emphasizing the relevance
of these pollutants as vectors and also revealing how smaller particles
have a higher accumulation of metals.[33]
Table 2
Different Chemical Elements Found
in Particles Deposited on the Inorganic Membranes after Filtrationa
√ Refers to the presence
of the element.
√ Refers to the presence
of the element.These heavy
metals can have several different effects, depending
on the specific metal and its concentration and speciation, including
neurological disorders and muscular diseases.[34] In addition, some masks have titanium dioxide nanoparticles bound
within the fibers, as this compound exhibits antimicrobial properties.[35,36] Research has shown that such nanoparticles can cause oxidative stress
and have a genotoxic effect.[37]Particles
containing high percentages of iron (Fe) have been observed
as part of larger particles (Figure ) and as part of fibers. The fibers also contained
Si on their structure (Figure ). DPFMs usually have nose strips that may be made of steel,
and possibly PVC/PE.
Figure 7
Particle on membrane containing Fe. (A) SEM-generated
image, (B)
false color map for elemental Fe.
Figure 8
Fiber
on membrane containing Fe and Si. (A) image generated by
the SEM, (B) false color map for elemental Fe. (C) false color map
for elemental C and (D) false color map for elemental Si.
Particle on membrane containing Fe. (A) SEM-generated
image, (B)
false color map for elemental Fe.Fiber
on membrane containing Fe and Si. (A) image generated by
the SEM, (B) false color map for elemental Fe. (C) false color map
for elemental C and (D) false color map for elemental Si.Complex particles with high percentages of Fe and traces
of many
different heavy metals were found in NHS samples. The elemental scanning
of one of these particles gave concentrations of 3.65% of As, 3.47%
of Cd, 3.73% of Cu, 4.71% of Hg, 3.96% of Ni, 5.65% of Pb, and 4.92%
of Sn, among others. Similar compositions were found in particles
of the same characteristics (Figure 62S in the Supporting Information).The particles found after
filtration of the blank samples presented
mostly compositions of silica with other elements in low concentrations
(like 0.29% of Cl), but not as complex as the ones found with the
submersion of DPFMs, and no heavy metals were detected. The number
of particles found was significantly lower than the leachates that
had DPFMs submerged (Figures and 5).
ICP-MS
Results
For ICP-MS analysis
of samples, a full external calibration was performed to determine
the analyte concentration, and reagents and procedural blanks were
used prior to and after analysis of the samples to assess any potential
carryover. All QC determinants for As, Cd, Cr, Co, Cu, Mo, Ni Pb,
Sb, Ti, and Hg passed the acceptance criteria. For blank samples,
all values possess concentration values below the analytical detection
limits, except for Cu, Mo, Pb, and V. Subsequently, any positives
in samples were blank-subtracted and -corrected. Table shows the leachable heavy metals
from the DPMFs (converted to 1 mask per liter). Three masks were added
to 250 mL of deionized water. To convert values to 1 mask per liter,
the instrument values (Table T1S) were
blank-corrected and then divided by a factor of 12.
Table 3
Results of Metals Leached from Medical
DPFMs in μg/La
sample identity
As
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Ti
μg/L
Geji
NDb
ND
ND
0.015
0.200
0.083
0.018
0.005
0.312
0.001
Duronic
ND
0.001
ND
ND
0.201
0.006
0.015
0.001
0.011
0.001
Baltic
ND
ND
0.003
0.029
0.093
0.003
ND
ND
2.413
0.001
Omnitex
ND
0.001
ND
ND
4.676
>0.03
0.025
0.005
0.373
0.002
Soyes
ND
ND
ND
0.033
0.033
>0.03
0.006
ND
0.149
ND
NHS
ND
ND
ND
ND
0.065
>0.03
0.007
ND
ND
0.001
Raw data can be seen in the Supporting Information with the LOD and calibration
curves.
ND, not detected
(below the detection
limit, please see the Supporting Information Figures 46S–58S).
Raw data can be seen in the Supporting Information with the LOD and calibration
curves.ND, not detected
(below the detection
limit, please see the Supporting Information Figures 46S–58S).The metal levels found in the DPFM leachates were all typically
low levels, the majority being subparts per billion (ppb) levels,
and some not detected altogether (As and Hg). The highest metal determinates
were found to be Cu (Omnitex mask leachate at 4.68 μg/L) and
Sb (Baltic mask leachate at 2.41 μg/L).Overall, FFP2
DPFMs appear to have significantly lower levels of
trace metals than that of recently studied Type IIR masks analyzed
in the previous publication. Upon the comparison of Sb and Pb levels
present in FFP2 DPFM leachates and Type IIR DPFMs, Sb ranged from
0.01–2.41 μg/L and Pb >0.001–0.005 μg/L
in FFP2 type, whereas in Type IIR, it had concerning levels of Sb
ranging from 27.8–98.25 μg/L, and Pb values up to 1.70
μg/L, indicating a significant increase in emission in Type
IIR DPFMs (values converted from a previous publication to 1 mask
per liter by dividing values by 4).Again, analysis for the
emission of toxic metals Cd, Ni, and Cr
proved negligible for the DPFMs in this study. Cd was found at very
low parts per trillion (ppt) level in Duronic and Omnitex brand leachates,
with a slight elevation of chromium detected in Geji, Soyes, and Baltic
samples (0.015–0.033 μg/L). Nickel was found in all masks
apart from Baltic, likely to arise from the metal wiring parts in
the mask, but this was still at very low levels (0.006–0.025
μg/L).
LC–MS Results
The organic
contaminates present in the leachate were assigned identity based
on accurate mass data, ms/ms fragmentation information, and analyst
discrimination. Polymeric species of caprolactam, −(C6H11NO) (a precursor for nylon
6 or 66 with peaks between 7.5 and 9.5 min [m/z (209), 227, 249], 13.5 min [m/z 322,340 and 362], 14.6 min [m/z 435, 453 and 475], 15.3 min [m/z 548,566, and 588], and 15.7 [m/z 679/701]), was found in brands Duronic, Geji, NHS, and
Soyes. These were not identified in Baltic, Omnitex, and blank samples
(Table and Supporting
Information Tables T1S and T2S and Figure ).
Table 4
Leachable Organic
Compounds from DPFMs
Identified by LC–MS Accurate Mass; ND Refers to Analyte Not
Being Detected, √ Indicates Its Presencea
ND, not detected.
Figure 9
Total ion chromatogram
(TIC) (1–7) from the LCMS analysis
of the leachate of all samples and blank. Omnitex (5) appears to release
the least number of organic species and its TIC has a similar appearance
to that of the blank sample (1). Caprolactam polymeric species, PEG
polymers, and detergent molecules have been labeled on associated
chromatograms.
Total ion chromatogram
(TIC) (1–7) from the LCMS analysis
of the leachate of all samples and blank. Omnitex (5) appears to release
the least number of organic species and its TIC has a similar appearance
to that of the blank sample (1). Caprolactam polymeric species, PEG
polymers, and detergent molecules have been labeled on associated
chromatograms.ND, not detected.Ions consistent with polyethylene glycol (PEG) polymers (homologues
series separated by m/z 44) and
triton-reduced (m/z 455, 527) nonionic
surfactants were observed in all sample leachates but not in the blanks,
indicating evidence of organic substances being released from the
DPFMs. Similar organic compounds were present in Type DPFMs analyzed
in a previous study.PEG-like and detergent compounds are likely
to be associated with
plasticizers, applied to modify the plastic properties during the
manufacture of the DPFM plastic materials, while the caprolactam oligomers
originate from nylon-6,6 precursors, used in the manufacture of the
elasticated parts of the masks.[38,39] All these organic leachable
compounds, commonly found in the textile industry, have known environmental
impacts associated, and thus, the release from DPFMs is an additional
cause of concern.[40,41]Also, the nonionic surfactant
Triton X was detected. In 2012, this
detergent was included in the “List of substances of very high
concern” of the Registration, Evaluation, Authorization, and
Restriction of Chemicals by the European Chemicals Agency, mandating
industries, including pharmaceuticals, its replacement by January
2021.[42] One of the products resulting from
the degradation of Triton X has been demonstrated to have hormone-like
properties that might affect organisms in the environment, and thus,
is also a cause of concern.[43]Other
compounds, like PEG, were present after LC–MS analysis.
Although PEG is considered biologically inert, approximately 72% of
the population has been proved to have PEG antibodies.[44] Because of this, allergies and hypersensitive
reactions are an increasing concern.[45,46]
Conclusions
FFP2 and Type IIR medical-grade DPFMs have
been shown to release
micro and NP particles and fibers when submerged in water. Characterization
of the masks determined that these particles and fibers were most
likely made from polypropylene. Among the two designs of masks researched,
FFP2 masks were found to emit more fibers than Type IIR masks with
significant amounts of additional microplastic particles being released
from foam nose cushions present on one of the FFP2 brand masks.In addition to the plastic particles and fibers, the masks have
also been shown to emit heavy metals (such as arsenic, antimony, mercury,
lead, tin, and titanium), showing their potential as a serious contamination
source because of their widespread use as a result of the COVID-19
pandemic. The levels of these pollutants are lower than those previously
published for nonmedical DPFMs, and thus, medical DPFMs could present
a lower risk. Nevertheless, more analysis should be performed in order
to clarify the origin of these compounds and whether the manufacturing
process must be revised and improved.The presence of particles
containing heavy metals in the masks
is of particular concern as it is unknown how strongly they are bonded
to the mask fibers. The potential leaching of these particles during
the use of the masks, or when the masks are within the environment,
requires further investigation. The bioaccumulation properties of
the detected heavy metals are a cause of concern because of the great
amount of medical DPFMs entering the environment when disposed. ICP-MS
analysis results confirmed traces of heavy metals (antimony up to
2.41 μg/L and copper up to 4.68 μg/L). LC–MS analysis
results identified polar leachable organic species related to plastic
additives and contaminants, polyamide-66 monomer and oligomers (nylon-66
synthesis), surfactant molecules, and PEG.These results claim
for stricter regulations to be put in place
regarding the manufacturing and disposal of DPFMs. Also, a complete
investigation must be done to clarify the extent of the risks and
the potential impacts of the fibers and particles released when using
these items and when they enter the environment.
Authors: Ana L Patrício Silva; Joana C Prata; Catherine Mouneyrac; Damià Barcelò; Armando C Duarte; Teresa Rocha-Santos Journal: Sci Total Environ Date: 2021-06-17 Impact factor: 7.963
Authors: Steffen E Eikenberry; Marina Mancuso; Enahoro Iboi; Tin Phan; Keenan Eikenberry; Yang Kuang; Eric Kostelich; Abba B Gumel Journal: Infect Dis Model Date: 2020-04-21
Authors: Enikő Mészáros; Attila Bodor; Ádám Szierer; Etelka Kovács; Katalin Perei; Csaba Tölgyesi; Zoltán Bátori; Gábor Feigl Journal: J Hazard Mater Date: 2022-06-01 Impact factor: 14.224