Chemosphere 287 (2022) 132172

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Characterization and source analysis of heavy metals contamination in

microplastics by Laser-Induced Breakdown Spectroscopy
Xi Chen, Shujat Ali, Leiming Yuan, Fengyi Guo, Guangzao Huang, Wen Shi, Xiaojing Chen *
College of Electrical and Electronic Engineering, Wenzhou University, Wenzhou, 325035, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Multi-metals detection of individual

beached MPs was accomplished.
• The origins of metals in MPs were
demonstrated by specificity and
generality.
• The statistical analysis of metals was
used to determine the contaminants
sources.
• It is a non-destructive and promising
strategy for plastic-metal interaction
research.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Michael Bank The increasing presence of microplastics in marine environment is a critical issue and the plastic-metal
contamination has received much attention. However, conventional methods for heavy metal determination
Keywords: are time-consuming, need sample pretreatments, require a strict operation environment, or have high limits of
Microplastics detection. In this study, heavy metals contaminated microplastics samples collected from a remote coral island
Heavy metals
were quantified and analyzed by using Laser-Induced Breakdown Spectroscopy (LIBS). The characters of the
Original source
trace metals in microplastics were used to determine the sources of the contaminants, and the potential origins of
LIBS
the metals were demonstrated from the statistical analysis. LIBS is a facile and non-destructive trace analysis
technique and the strategy led to rapid and multi-metals detection of individual samples. Heavy metals such as
copper (Cu), lead (Pb), iron (Fe), cadmium (Cd), zinc (Zn), manganese (Mn), chromium (Cr) were detected and
quantified in the individual microplastics samples. The findings showed that LIBS is a promising strategy for the
characterization of microplastics and for the analysis of the source of heavy metals contaminants present in the
microplastics particles.

1. Introduction
Microplastics (MPs) are considered as a threat to marine environ­
ment, especially they play a key role in the migration of heavy metals
and act as an important carrier in the environment (Turner et al., 2020;
Bradney et al., 2019; Godoy et al., 2019; Leiser et al., 2020). Several
studies have been reported about the absorption, transport and storage
of metal contaminants (Dobaradaran et al., 2018; Vedolin et al., 2018).
Previously, various methods such as ICP-MS (Carbery et al., 2020),
ICP-OES (Martins et al., 2020), auger electron spectroscopy, X-ray

* Corresponding author. Address: Building 1, North Campus, Wenzhou University, Chashan University Town, Wenzhou City, Zhejiang Province, 325035, China.
E-mail address: cx@wzu.edu.cn (X. Chen).

https://doi.org/10.1016/j.chemosphere.2021.132172
Received 24 March 2021; Received in revised form 26 August 2021; Accepted 3 September 2021
Available online 4 September 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
X. Chen et al. Chemosphere 287 (2022) 132172

photoelectron spectroscopy and energy-dispersive X-ray spectroscopy protect the marine environment.
(Idris et al., 2011) have been applied for the determination of heavy
metals contamination in MPs. Although these methods can be applied 2. Materials and methods
for the analysis of heavy metals contamination, they have some short­
comings such as destruction of samples and time-consuming sample 2.1. Collection of MPs samples
pretreatment (Ren and Wang, 2009). Furthermore, a large number of
samples are required to accumulate to a certain amount of metal pol­ Samples were collected from Dong Island (16◦ 40.5′ N, 112◦ 44.2′ E),
lutants to reach the limitation of instrumental detection (Zhong et al., located in the South China Sea, China. The island is used for army
2011). Hence, it is crucial to develop a facile, non-destructive and effi­ garrison with limited waste disposal. Three natural accumulation zones
cient method for analyzing heavy metals contaminations in MPs. along the island were selected for MPs sampling. The sampling sites
Interestingly, Laser-Induced Breakdown Spectroscopy (LIBS) can be were labeled as D1, D2 and D3 (Fig. 1). Waste generated by this island is
directly used to detect heavy metals and has been proven its mature burned or dumped in a designated location. This island is surrounded by
applications for multi-component analysis （Bana Ee and Tavassoli, a coral sand beach with a tiny gradient. The MPs waste accumulates on
2012; Su et al. (2021); Xu et al. (2021). In the latest research, LIBS has beaches resulting in a constant import and export of MPs from the ocean.
been used for simultaneous analysis of multiple metal elements on in­ The upper surface of the layer about the thickness of 3 cm was removed
dividual MPs (Chen et al., 2020). This non-destructive and trace analysis by a stainless steel shovel to collect MPs sediment, and all the potential
technique needs a small amount of sample for analysis and its detection flake plastic particles with the range of 1–5 mm were sorted by the
time is short (millisecond level). Generally, different kinds of metals sample size. The beached MPs were preferred for they were likely
accumulate in environmental MPs such as exchangeable metals, reduc­ accumulate more trace metals on plastics with longer residence times.
ible metals, oxidizable metals and residual metals (Prunier et al., 2019). Approximately 150 samples were collected from each site, and a total of
Significantly, LIBS technology can be applied for samples analysis in 450 samples were obtained from the 3 locations. These samples were
different forms such as solids, liquids, gases and aerosols (Hahn and respectively put into small glass containers, transferred to the laboratory
Omenetto., 2010; Harmon et al., 2005) at a trace level (Osman and and oven-dried at room temperature.
Kloas, 2010; Hussain and Gondal, 2008). Hence, the LIBS technology is
capable of detecting trace amounts and different forms of metals in
2.2. Component identification by ATR
particular MPs. The two main possible sources of heavy metals
contamination of MPs are; 1) the metals may come from the
The FTIR coupled with Attenuated Total Reflectance (ATR) was used
manufacturing process (additives) and 2) as a result of environmental
to identify the compositions in MP samples; the measurements of each
sorption (Zou et al., 2020; Gao et al., 2019). Some studies have
potential particle were performed by Bruker Vertex 70 spectrometer.
demonstrated that the metals are added in plastics manufacturing as
The spectral background was measured against air with the same
colorants (Mn, Cd, Pb, Ti), fillers (Ba, Ca, Mg) and catalysts (Mo, P, Pb,
setting, and the spectra collection was performed with OPUS 7.5 soft­
Sr, Zn) (Turner and Filella, 2021). Furthermore, the discarded MPs can
ware. After the spectral dataset was collected, several spectral pre­
adsorb metals such as Pb, Cu, Sn, Mo, Sr from the environment, which
treatments including smoothing and baseline correction were applied to
are naturally occurring in the marine environment (Brennecke et al.,
improve the signal to noise ratio (SNR) of the spectra. Consequently, the
2016). Currently, there is no standard or accepted method for accurately
influences of some uncertain noises produced from the spectral trans­
analyzing the origin of heavy metals contamination in MPs. LIBS tech­
formation, physical scattering effects and manual operations were
nology can be applied to develop a simple and rapid method for the
reduced. In this study, the sample validation was realized by OPUS by
multiple detections of metals contamination in individual MPs samples.
using the assigned reference spectra in the software. The composition of
The potential source of heavy metals can be studied by the statistical
the plastic sample was identified according to the characteristic peaks
analysis of heavy metals contamination on the same site of single MPs
and by using the similarity of the matched spectral library. The standard
sample. In the aspect of statistical analysis, the generality reflects the
matching rule of the spectral library was implemented for the highest
universality of samples. The universality source as the metal accumu­
accuracy (higher than 80%).
lated from the surrounding environment can be revealed by the gener­
ality. Furthermore, the statistical analysis of the specificity reflects some
special characteristics of individual samples and the source of the metal 2.3. Trace metal analysis by LIBS
from which it is originated during manufacturing process.
In this work, the LIBS was applied to quantify the heavy metals The LIBS framework was consist of a Q-switched Nd:YAG laser
accumulated on individual MPs. The samples were collected from 3 (model: Nano SG150–10, Litron Ltd., UK), a spectral instrument (model:
beaches along the coast of the South China Sea. The samples were Aryelle 150, LTB Lasertechnik Berlin GmbH., Germany) and a moving
analyzed by ATR-FTIR technology. This technology works well on the stage (model: SC300-1A, China), as shown in Fig. 2. The Q-switched
identification of irregularly shaped MPs and the effect caused by the
non-suitable area can be neglected. The flake polyethylene samples with
the same thickness (1 mm confirmed by vernier caliper) were used for
the quantitative analysis of metals, these samples were supposed to
minimize the matrix interference of LIBS technology. The amount of
each metal was determined by using the linear relationship between the
intensity of the LIBS signal and the elemental concentration. The relative
intensity of finger-prints peaks in LIBS spectra was used to represent the
semi-quantitative analysis of the target metals. The method was suc­
cessfully applied for the simultaneous determinations of multi-metals in
individual MPs samples, and metals such as copper (Cu), lead (Pb), iron
(Fe), cadmium (Cd), zinc (Zn), manganese (Mn) and chromium (Cr)
were detected and quantified correspondingly. The sources of the
detected metals and their potential origins were described by using
statistical analysis and characters of the trace metals in the micro­
plastics. These findings could apply to implement necessary measures to Fig. 1. The sampling sites along the beach of the Dong Island.

2
X. Chen et al.
Fig. 2. LIBS system for metal elemental analysis of individual MPs.
laser excited the short-pulse high-energy light, whose propagation di­
rection was deflected by a 45◦ - posed reflection mirror and then pro­
jected onto a beam splitter, and thus produced two propagating
directions. One beam (approximately 10% light energy) was transferred
into the energy meter which regulated the pulse energy; the other beam
was converged by a convex lens (with a diameter of 30 mm and focal
length of 100 mm) and projected onto MPs sample on the moving stage
for sample analysis. During sample analysis, the laser beam was focused
on each flake by fine-tuning the position of a 3-axis stage. Plasma
emission from the sample’s surface was captured by a light collector
accessory and transferred into a spectrograph by an optical fiber to
digitalize the spectral signals. Preliminary attempts were conducted to
set the laser parameters for this work: pulse energy 1064 nm@50 MJ,
duration time 6 ns and repetition rate 5 Hz. Spectral scanning parame­
ters were adjusted as resolving power of 6000 and 32,071 pixel points in
the spectral range of 200–800 nm. LIBS spectrum was calculated from
the repeated readings of each sample over 10 times. Five repetitions
were operated continuously for each sample, and their averaged spec­
trum was calculated from all the repeated readings as the final LIBS
spectrum of the sample. Standard normal variate (SNV), moving
smooth, and demean centralization (MC) were conducted to improve the
spectral SNR.
In this work, it was found that the accuracy of the LIBS technology
depends on the thickness of the sample, not by the length and width of
the sample. The length and width of all the samples were less than 5*4
mm, and most flake polyethylene samples were about 3*2 mm. Poly­
ethylene (PE) was chosen as the target sample as they are the more
common sample in this sample beach. The flake PE sample with the
same thickness was chosen for the quantitative analysis of metal; the
flake sample with the same form was supposed to decrease the matrix
interference of LIBS technology produced from the instrumental and
physical scattering. The concentration of each particular element was
determined by the LIBS signal intensity due to the linear relationship
between the intensity of LIBS signal and the elemental concentration.
The process of LIBS including ablation, atomization, excitation, ioniza­
tion and recombination is quite complex and difficult to reproduce. As a
result, each LIBS signal usually exhibits unpredictable variations, which
usually leads to poor precision and sensitivity. Quantitative measure­
ment in a complex matrix is still an issue in LIBS analysis and has been
considered the matrix interference of this technique. The most common
method to achieve the quantitative results in the LIBS is the construction
of calibration curves with reference samples. As the MPs samples in the
actual beached environment were in diversity, there was no possible
method for the construction of calibration curves by static simulating
experiment. Several pretreatments, including de-mean centering and
3
Chemosphere 287 (2022) 132172
multiple scattering correction, were used to minimize the matrix inter­
ference in the spectra of MPs caused by spectral transformation and
manual operations. Although pretreatments were carefully performed
on the LIBS spectra to remove these interferences, complete removal was
impossible. Here in this work, a strategy has been proposed for a semi-
quantitative analysis of heavy metals contamination in MPs.
3. Results and discussion
3.1. Sample statistical characteristics
The sampled MPs were in different shapes as fragments, fiber,
granule, film, and foamed. The sizes of the collected MPs samples were
in the range of 0.5–5 mm. The MPs samples were divided into four
grades based on their size as: <1 mm, 1–2 mm, 2–3 mm and 3–5 mm.
Fig. 3a shows the distribution of MPs sizes from three sampling sites. In
general, the highest abundance of the MPs was in the size of 1–2 mm
which accounting for nearly 40%. All these samples were confirmed by
ATR-FTIR in the wavelength range of 4000–600 cm− 1 with the spectral
resolution of 4 cm− 1, and their composition was identified by OPUS 7.5
software. Commonly, the discarded MPs are mainly composed of Poly­
ethylene(PE), Polypropylene(PP), Polyethylene terephthalate (PET),
Polystyrene (PS), rayon and acrylic. In this work, the flake samples
confirmed by FTIR were mainly composed of PE and PP (71.8% PE and
28.2% PP). The flake PE with the same thickness was selected in this
quantitative analysis to decrease the matrix interference as much as
possible. The dominant colors of plastics samples from the three beaches
were mainly white and translucent, but some appeared with a yellowing
or browning effect. The color distribution of all MPs is reported in
Fig. 3b. The percentage of each color attribute was in the order of yellow
(32%) > white (24%)> others (19%) > transparent (25%). The carbonyl
functional groups were identified by FTIR spectra of the environmental
flake PE samples. The carbonyl index was used to characterize the
degradation degree of the environmental sample. Based on the FTIR
spectra of the samples, the transparent or yellowish samples have a low
level of carbonyl index, while the yellow or black samples have a high
level of carbonyl index. It was inferred that the degree of yellowing or
darkening effects were associated with an increase of the carbonyl index,
which indicated the degradation of the sample.
3.2. Metals distribution in beached MPs
LIBS analytical technology is virtually sensitive to all elements and is
suitable for trace detection of heavy metals present in individual MPs
samples. The flake PE plastics were the most abundant waste in Dong
Island. Hence, the LIBS spectra of typical flake PE MPs samples were
recorded in the range of 200–820 nm; the profile of their averaged
spectra is presented in Fig. 4a. The C, N, H, and O elements found in the
spectrum were accounted for the components of PE plastics, and some
metal elements were also identified clearly in the LIBS spectra through
the pulsed peaks. The metal elements in individual environmental MPs
in the range of 200–550 nm are shown in Fig. 4b. By analysis of the
peaks position and intensity, it was found that the beached MPs particles
contain a large number of heavy metals, including copper (Cu), lead
(Pb), iron (Fe), cadmium (Cd), zinc (Zn), aluminum (Al), manganese
(Mn) and chromium (Cr). The intensity of LIBS signal was related to the
amount of trace metals contained in each MP sample and the amount of
heavy metals was predicted from the emission intensities.
In this work, 30 flake PE were chosen from each location, and a total
of 90 MPs particles were collected from the 3 locations for analysis of
LIBS spectra. Fig. 5 represents the LIBS spectra of 4 PE MP samples
collected from different beaches. The LIBS spectra demonstrated the
presence of several metals such as zinc (Zn), iron (Fe), calcium (Ca), lead
(Pb), cadmium (Cd), copper (Cu), aluminum (Al), magnesium（Mg),
nickel (Ni)，chromium (Cr) and manganese (Mn). Results showed that
the distribution of metal elements was varied significantly from one
X. Chen et al. Chemosphere 287 (2022) 132172

Fig. 3. (a) Size distribution and (b) color distribution of MPs from the three sample-collection sites. (For interpretation of the references to color in this figure legend,
the reader is referred to the Web version of this article.)

Fig. 4. (a) The LIBS spectra of typical individual beached PE MPs (b) the zoom spectra of Fig. 4a in range of 200–550 nm.

Fig. 5. (a) LIBS spectra of the heavy metals detected in 4 individual MPs particles sampled at different sites. (b) Types distribution of heavy metal contamination on
the bulk of individual MPs.

individual sample to another. These flake MPs were categorized into 5
groups according to the number of metals they contain, such as >8 el­
ements, 6–8 elements, 4–5 elements, 1–3 elements, and none element.
According to the statistics, it was found that the beached samples with a
range of 6–8 elements were the most abundant (36%), the 4–5 elements
and >8 elements accounted for 35% and 18% respectively, and the 1–3
elements samples were 10%. Besides, there were also nearly 4% NF
(metals not found) samples as the metal peaks were immerged in low
SNR LIBS spectra. Some unqualified environmental samples (with an
uneven or rough surface) resulted in low SNR of the LIBS spectra. The
various types of metals on the surface of individual MPs demonstrated
that the metals were either inherited from plastic manufacturing or
derived from the environment.

4
X. Chen et al.
3.3. Source analysis of heavy metals
LIBS technology was applied to quantify the level of the heavy metals
on individual MPs samples at different sites in Dong Island. The quan­
titative analysis of these heavy metals was performed by calculating the
intensities of their specific emission lines, which were linearly propor­
tional to their abundances in MPs particles. Seven typical metals
including Fe, Pb, Cu, Zn, Cd, Cr and Mn were detected and quantified.
The intensities of the emission lines related to Fe (259.2 nm), Pb (405.8
nm), Cu (324.3 nm), Zn (213.7 nm), Cd (360.4 nm), Cr (430.2 nm), and
Mn (403.3 nm) respectively are shown in Fig. 5b. The peaks intensities
of the heavy metals were normalized to the C element (assigned to the
carbon functional group) at 247.9 nm in this semi-quantitative analysis.
Although LIBS has been widely used to quantify the content of heavy
metals, this technology is influenced by the negative matrix interference
produced from the physical scattering of the sample. Owing to the
diverse MPs samples there was no possible method to remove the in­
terferences completely. Thus, the relative intensity of finger-prints peaks
in LIBS spectra was used to represent the semi-quantitative analysis of
the target metals.
The trace level of heavy metals in the MPs samples collected from the
3 beaches was characterized by LIBS spectra, the detail is listed in
Table 1. In addition, the statistical analysis of the heavy metal level is
expressed as the mean ± SD values, the generality of a heavy metal
accumulated in these samples is represented by the mean parameter,
and the specificity of heavy metal accumulated in these samples is
represented by the SD parameter. The results showed that the metals
accumulated on MPs were varied significantly between locations, and
this was consistent with a recent report (Marsic-Lucic et al., 2018).
Comparatively, samples collected at location 1 were found to have a
higher level of Fe with a mean value of 60.46, the mean values for
samples collected from locations 2 and 3 were 36.65 and 38.56
respectively, while Cd element was present in the lowest level with a
mean value of 18.33. The MPs samples collected from location 2 have
the highest level of Cr, Cd, and a same level of Mn, compared with the
samples from locations 1 and 3.
The accumulation level of heavy metals in MP particles from the
environment was relatively low in the long-term disposal. In general, the
low mean intensity indicated that the metal was concentrated from the
natural environment (represent a local pollution problem), while the
high mean intensity indicated that the metals resulted from the plastics
manufactures (Vedolin et al., 2018). Interestingly, some MPs particles
showed significantly different contents of heavy metals; even the sam­
ples were collected from the same place with the same external envi­
ronment. These differences indicated that metals were not related to the
migration process in the environment but inherited in MPs, and the
different contents were reflected by the higher SD parameter. Specif­
ically, the amount of Zn in the individual MPs showed a higher SD above
35.79, the same as the Pb element (above 14.68) in MPs sampled from 3
locations (Table 1). These higher SD differences can be clarified by some
samples with a higher initial metal amount, and others with a
no-intrinsic metal amount. So, a higher SD confirmed that the metal was
originated from an anthropogenic source. For example, the statistical
analysis of the Zn element in the MPs sample from location 3 in Table 1
exhibited a higher mean value (80.91) and higher SD (40.07). Despite
these typical statistical characters (with higher mean and higher SD), Zn
Table 1
Metal levels (mean and standard deviation; n = 30) in flake PE MPs sampled from 3 beaches along the South China Sea.
Sample’s attributes Cu Fe Zn
Mean SD Mean SD Mean
Location1 15.32 4.79 60.46 8.23 55.85
Location2 10.25 6.66 36.66 6.87 65.54
Location3 12.35 5.57 38.56 6.24 80.91
Note: Statistical analysis of elements in Mean intensities: average amount; SD: standard deviation over particles.
Chemosphere 287 (2022) 132172
was mainly a consequence additive as heat or UV stabilizers in the MP
formulation process (Prunier et al., 2019). Pb and Cd elements varied
strongly with high SD in all three sample locations, indicated that these
metals were used as colored pigments additives in some plastics.
As shown in Table 1, some heavy metals were present in very low
levels. It seemed that these heavy metals (carried by MPs with low SD)
were attributed to a similar source as the accumulation from the same
surrounding environment (Massos and Turner, 2017). In this research,
the Cu in all three locations was displayed with a low mean (below
15.32) and low SD (below 6.66). The results indicated that Cu was
derived from the marine environment. Meanwhile, the Fe element with
low SD (below 8.23) indicated that this metal shared a similar natural
source. The Cu and Fe contaminants in MPs may have been derived from
industrial activities in the corresponding mainland region. The statisti­
cal information showed that some heavy metals in MPs have compli­
cated sources, as the Cr element with a high mean of above 60.33
indicated that this metal comes from intrinsic additives. Meanwhile, the
Cr with the a low SD of below 9.69 showed that it accumulates from the
surrounding environment. Therefore, the Cr in MPs was like to come
from both anthropogenic and natural sources as it displayed a strong
positive correlation with the high level and the low variance. Table 1
showed that the Mn in the samples collected from three locations has a
relatively high SD of above 14.78 but a low mean of below 24.78. This
confusing phenomenon of the specific element was due to the lack of
good reproducibility in LIBS technology; the trace level of Mn was
represented by a peak at 213.65 nm was sometimes submerged in the
background noise. Therefore, the source of the Mn element needed to be
further explored. In conclusion, it was found that the beached samples
from three locations were moderately contaminated with Cu and
strongly contaminated with Cr and Fe. It was inferred that Cu and Fe
were accumulated due to environmental sorption which commonly oc­
curs in the marine environment, and the presence of Zn, Pb and Cd
resulted from the additives in plastics manufactures. The Cr element in
MPs was likely to come from both anthropogenic and natural sources.
The results indicated that some human activities include industrial,
agricultural, port operations and maritime in the corresponding main­
land region were account for the metal contamination.
The most fragments sample detected by LIBS was transparent and
white, the colored fragments sample was less than 25%. Compared with
the transparent microplastic, the red and orange colored samples have
the higher content in Pb and Cd metal elements, the yellow sample has
the higher content in Cr element. These kinds of metals may be related to
the colorants added during plastic production. The relationship between
sample color and Pb and Cd, Cr content has been added in Table 2 below.
3.4. Heavy metals accumulation of the beached MPs
Several studies have reported that the MPs can trap metal pollution
from the environment (Isabel et al., 2019; Vedolin et al., 2018), and a
higher amount of heavy metal occurs on the surface of the MPs than the
surrounding (Lang, M et al., 2020). Some reports have shown that the
beached particles have a higher tendency to adsorb metal after a long
period of degradation (Mao et al., 2020; Gao et al., 2019). In this study,
the PE sample was found to have a higher sorption capacity for some
metals and tended to accumulate these metals. Specifically, the level of
Fe in the beached or degraded MPs samples was higher than that in the
Pb Cd Cr Mn
SD Mean SD Mean SD Mean SD Mean SD
44.35 30.43 14.68 18.33 12.39 60.33 8.39 15.33 15.39
35.79 40.56 19.48 40.73 20.78 75.73 6.78 22.73 14.78
40.07 34.43 22.94 32.78 12.69 66.78 9.69 24.78 16.69
5
X. Chen et al. Chemosphere 287 (2022) 132172

Table 2
The mean content of Pb and Cd, Cr element in different colored MPs sampled from 3 beaches along the South China Sea.
Color Red Orange Yellow Transparent
Element
Pb Cd Cr Pb Cd Cr Pb Cd Cr Pb Cd Cr

Location1 33.24 30.57 48.65 30.26 29.38 46.67 25.77 19.90 70.67 20.13 16.22 44.23
Location2 47.45 55.28 50.34 50.89 60.35 49.23 36.56 32.24 88.35 30.78 28.56 43.78
Location3 39.79 48.97 49.46 42.45 45.78 52.79 30.36 29.45 78.23 26.56 23.77 49.90

relatively new samples (smooth surface); the difference was around

tenfold or greater. These findings showed that the MPs could absorb
heavy metals and carry them in long distances. All the flake PE were
categorized by FTIR, and the spectra indicated that the beached pellets
were associated with an increasing tendency in the carbonyl index,
which indicated the degradation of the samples. Fig. 6 shows that the
level of Fe in MPs was linearly proportional to the degree of MPs
degradation. It is clear that the environmental sample with a lower value
of carbonyl index (below 1.5) contains less contamination of Fe (at the
level of 30), while samples with a higher value of carbonyl index (above
3.5) have more Fe contamination (almost 80). It can be inferred that the
increase of metal concentrations on plastic debris is related to the
degradation and weathering layers, which generate new binding sites
for metal accumulation. The surface area of the aged MPs was increased
with being cracked and crushed during the natural weathering, which
made it easy to adsorb more metal ions and to balance the charge. The
biomass adheres to the surface of the aged particles also enhanced the
adsorption of heavy metals. Besides, some other metal elements such as
Cu and Zn in MPs exhibited the same tendency. However, low linearity
was observed in the level of these elements and degradation degree of
MPs.
In this study, multi-metals elements on individual MPs samples (the
metals intrinsic from the samples or derived from the environment) were Fig. 6. Relationship between the amount of Fe absorbed on MPs and carbonyl
index of degradation PE sample.
assessed by LIBS technology. The accumulation patterns of plastic-metal
interaction remained relatively unexplored as the plastic-metal inter­
action can be influenced by several combined environmental conditions Declaration of competing interest
such as degree of degradation, residence time and emission source.
Besides, the desorption processes can release the metals back into the The authors declare that they have no known competing financial
environment. The LIBS is a spectroscopic technique with the advantages interests or personal relationships that could have appeared to influence
of being non-destructive and free from sample pretreatment, making it the work reported in this paper.
easy to study the mechanism of plastic-metal interactions. Furthermore,
the strategy can be extended to learn how the environmental conditions Acknowledgments
influence the metal transfer process. It can track the complete process of
the adsorption and desorption in plastic-metal interactions research. This work was supported by grants from the Natural Science Foun­
dation of China (61805180) and Wenzhou science and technology bu­
4. Conclusion reau general project (G20200044) and the Natural Science Foundation
of Zhejiang (LQ20F030021).
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