Journal of Hazardous Materials 423 (2022) 127165

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Journal of Hazardous Materials

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Comparison of the ability of UV-Vis and UPLC-Q-TOF-MS combined with

chemometrics to discriminate recycled and virgin polyethylene
Zhi-Feng Chen a, Qin-Bao Lin a, *, Ben Dong b, Huai-Ning Zhong b, c, Zhi-Wei Wang a
a
Key Laboratory of Product Packaging and Logistics, Packaging Engineering Institute, Jinan University, Zhuhai 519070, China
b
Guangdong Provincial Key Laboratory of Import and Export Technical Measures of Animal, Plant and Food, Guangzhou Customs Technology Center, Guangzhou,
Guangdong 510623, China
c
China Certification and Inspection Group Guangdong Co. Ltd, Guangzhou 510623, China

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

Editor: Dr. C. Baiyang A growing attention is attracted to the use of recycled plastics as food contact materials, and its chemical safety
research and discrimination approach are indispensable. In current study, ultraviolet-visible spectrometry (UV-
Keywords: Vis) and ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-
UPLC-Q-TOF-MS MS) were used to provide spectral and mass fingerprinting for polyethylene (PE). Coupling with chemometrics,
UV-Vis
two methods were developed to discriminate recycled and virgin PE. UV-Vis combined with chemometrics could
Chemometrics
be a more accessible, simpler and faster approach. 237–331 nm in UV spectrum was regarded as marker region
Recycled polyethylene
Nonvolatile organic compounds selected by orthogonal partial least-squares discrimination analysis (OPLS-DA) and the accuracy of both cali­
bration and validation set could reach 100% in linear discrimination analysis (LDA) based on this region. Besides,
2314 ions were detected by UPLC-Q-TOF-MS and processed by MS-DIAL. 48 candidate chemicals were identified,
including ketone, esters, carboxylic acid, alcohols and phenols, amine, nitriles, aldehydes and others. Possible
origins of these compounds could be classified as plastic, food, drug, cosmetics and pesticide related. Many of
these compounds are highly toxic, especially pesticide related, indicating that recycling in closed loop or sorting
by the recycled plastic articles is very necessary if the recycled PE is going to be used as food contact material.

1. Introduction
The problem of plastic waste has drawn worldwide attention,
because its extensive accumulation in oceans, landfills and other
terrestrial compartments is harming wildlife, ecosystems and even
human health (Lithner et al., 2011). A new concept and development
model of circular economy (CE) was born, with three main actions, i.e.
the 3R’s principle: Reduction, Reuse and Recycle (Ghisellini et al.,
2016). Plastic packaging plays a great role in recycling as it accounts for
a large proportion of plastic requirements (Plastics Europe, 2019).
Decontamination is an important and unavoidable recycling process
before recycled plastics used in food packaging. Challenge test, a
method to measure the decontamination efficiency of recycling, has
been recommended by many institutions for food safety (EFSA, 2011;
FDA, 2006; ILSI, 1998), which is a red line to protect consumer food
safety. The realization of post-consumer polyethylene terephthalate
(PET) recycled for the food packaging undoubtedly brings great confi­
dence and motivation for other recycled plastics for food grade (EFSA,
2014; Lambre et al., 2021). However, the characteristics of diffusion and
adsorption of different plastics are various (Palkopoulou et al., 2016). To
control the migration safety of the final product, the same recycling
process and challenge test could not be applied for all types of recycled
plastics directly (EC, 2008). Polyethylene (PE) is an important member
of food contact materials, which has been demonstrated a very strong
ability in food protection (Chaliha et al., 2013). Therefore, application
of recycled PE in food packaging is an important task to promote the
recycling of PE. In order to achieve that recycled PE can be safely used as
a food contact material, its chemical safety after recycling is being
attracted more and more attention (Chen et al., 2020; Fuller et al., 2020;
Palkopoulou et al., 2016; Su et al., 2021; Welle, 2005). But there is still a
long way to go before food-grade PE can be widely recycled for food
contact material in the market.
However, driven by huge profits, recycled plastic that does not pass
challenge test might flows into the food contact material market,
causing huge economic losses to the companies that comply with the
regulations. Furthermore, high-risk substances migrated from the

* Correspondence to: Packaging Engineering Institute, Jinan University, Zhuhai 519070, China.
E-mail address: tlinqb@jnu.edu.cn (Q.-B. Lin).

https://doi.org/10.1016/j.jhazmat.2021.127165
Received 5 July 2021; Received in revised form 21 August 2021; Accepted 5 September 2021
Available online 12 September 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
Z.-F. Chen et al. Journal of Hazardous Materials 423 (2022) 127165

recycled plastic to the food in contact with them could pose a chronic or Table 1
acute threat to the food safety (Das et al., 2021; Su et al., 2021). Con­ Description of the polyethylene samples employed in this study.
taminants in recycled plastics mainly come from degradation products Materials Description Source
or residue of polymer, additives and their degradation, as well as input
R1 White pellet, from HDPE turnover box Company 1, Qingyuan,
contaminants, most of which are non-intentionally added substances and various HDPE bottles Guangdong, China
(NIAS) (Chen et al., 2020; Palkopoulou et al., 2016). Different from PET, R2 Celadon pellet, from LDPE films and Company 1, Qingyuan,
collected recycled PE might be contaminated with a wider range of bottles Guangdong, China
chemicals that may not be completely eliminated during the recycling R3 Black pellet, comprise of 90% LDPE Company 1, Qingyuan,
(films and bottles) and 10% model 7042 Guangdong, China
process (Palkopoulou et al., 2016). Therefore, in the context of the virgin PE
growing demand for recycled plastics, a method to monitor and identify R4 Gray pellet, from mixed PE materials Company 2, Suzhou,
recycled PE from virgin PE is necessary. Jiangsu, China
Probably because of the strong irritating odor of recycled PE (Fuller R5–R7 3 different batches with grayish yellow, Company 3, Dongguan,
clear white and greyish-green color, Guangdong, China
et al., 2020) or the limitations of the used analytical techniques, most of
respectively, with unknown previous
the current studies focus on the volatile and semi-volatile organic uses for commercial confidentiality
compounds using GC-MS (Chen et al., 2020; Dutra et al., 2011; Palko­ R8 Black pellet, comprise of 70% HDPE Company 1, Qingyuan,
poulou et al., 2016; Su et al., 2021). But actually, higher molecular (turnover box and bottles) and 30% Guangdong, China
weight substances in recycled PE should also be of concern (Palkopoulou model 7042 virgin PE
R9 Black pellet, comprise of 50% HDPE Company 1, Qingyuan,
et al., 2016). However, none of works studying the non-volatile organic (turnover box and bottles) and 50% Guangdong, China
compounds (NVOC) of recycled PE based on ultra-performance liquid model 5502 virgin PE
chromatography quadrupole time-of-flight mass spectrometry R10–R13 4 different batches with yellow, red, Company 4, Dongguan,
(UPLC-Q-TOF-MS) were found. The TOF mass analyzer could be the best black and green color, respectively, Guangdong, China
with unknown previous uses for
choice for untargeted analysis, providing accurate mass information of
commercial confidentiality
the precursor ion and corresponding fragments produced in the collision V1 Virgin LDPE Exxon Mobil, Avon, Texas,
cell. Combined with the mass spectrometry library, it is possible to USA
identify some of these substances. As for the establishment of discrimi­ V2 Virgin LDPE, model 4203 DOW, Mitterrand,
nation models, spectroscopy has been demonstrated its advantages in Michigan, USA
V3 Virgin HDPE, model P4406C Sinopec Group, Beijing,
many fields, such as food authenticity (Biancolillo et al., 2014; Di Anibal
China
et al., 2011; Márquez et al., 2016), species identification (Rios-Reina V4 Virgin LDPE CNOOC Shell, Huizhou,
et al., 2019) and geographical origins (Chen et al., 2008). Compared Guangdong, China
with UPLC-Q-TOF-MS, ultraviolet-visible (UV-Vis) spectrometry is a V5 Virgin LLDPE, model 7042 Sinopec Group, Beijing,
China
good alternative for the discrimination due to its advantage of
V6 Virgin HDPE Petroleum Authority of
simplicity, accuracy and easy accessibility. UV-Vis spectra contains Thailand (PTT), Bangkok,
abundance and complex information describing the overall signal from Thailand
many chromophores in the sample. The difference in UV-Vis spectra will V7 Virgin LDPE Siam Cement Group (SCG),
be associated with the changes in the compound composition present in Bangkok, Thailand
V8 Virgin HDPE, model HD-2200JP PTT, Bangkok, Thailand
the samples. The combination of UV-Vis spectra and chemometrics
could be a powerful tool to discriminate recycled plastics, but none of
studies focus on this.
Therefore, the aim of the current study is to discriminate recycled recyclers and no more details are available for confidential reasons.
and virgin PE by chemometrics using the data of UV-Vis spectra and To provide sufficient data for multivariate statistical analysis, every
UPLC-Q-TOF-MS, and compare the discrimination effectiveness of these two virgin samples and every two R1–R7 recycled samples were mixed
two methods. In order to establish the most effective identification together in 50:50% proportion respectively (For example, V1 and V2 are
method, orthogonal partial least-squares discrimination analysis (OPLS- mixed to form an V1–2 sample), thus a total of 36 virgin samples (28
DA) was used to explore the significantly different UV-Vis spectra region mixed and 8 initial samples) and 34 recycled samples (21 mixed and 13
between virgin and recycled PE groups. Non-volatile compounds initial samples) were obtained.
migrating from recycled and virgin PE to food simulants (95% ethanol)
were untargetedly screened by UPLC-Q-TOF-MS. With the help of the 2.2. Sample preparation
relevant databases, the detected features were identified as far as
possible, and their possible origins were searched as well. Before UV–vis spectra acquisition, a total of 2.0 g of sample (cylin­
drical pellets with a radius of approximately 3.4 mm and a height of
2. Materials and methods approximately 4.5 mm measured by a Vernier caliper) was placed in a
20 mL vial, and 10 mL ethanol were added as extraction solvent. Then,
2.1. Reagents and samples the vial was sealed, treated with ultrasound for 1 h, and followed by
heating at 70 ℃ for 48 h.
Ethanol (HPLC grade, Macklin, Shanghai, China). Acetonitrile (HPLC For UPLC-Q-TOF-MS analysis, a total of 2.0 g of the same sample was
grade, Macklin, Shanghai, China). Electronic balance (AL204, Mettler also placed in a 20 mL vial and immersed with 10 mL of 95% (V/V)
Toledo, Shanghai, China). Ultra-pure water machine (UPTC 10, Lichen ethanol, which is a fatty food simulant. Then, the vial was sealed and
Bangxi, Shanghai, China). Ultrasonic instrument (KQ5200DE, Kunshan subjected to migration test. According to EU regulation (EC, 2011), all
Ultrasonic, Jiangsu, China). Electric constant temperature drying oven migration tests were carried out at 60 ℃ for 10 days as an accelerated
(GZX-9420 MBE, Boxun, Shanghai, China). standard test for long time storage (> 6 months) at room temperature.
Eight types of virgin PE pellets (numbered as V1–V8) and thirteen Since the small size of the pellets, it is difficult to calculate the specific
types of recycled PE pellets (numbered as R1–R13) were collected from and accurate surface area, so the surface area to volume ratio is not
online purchasing platform or local manufacturers. These recycled pel­ calculated. Therefore, the main purpose of this experiment is to analyze
lets were treated mechanically, including crushing, cleaning, drying and the potential migrants from samples to simulant.
granulating by extrusion. Table 1 describes the PE samples employed in
the experiment, but some of them came from distributors rather than

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Z.-F. Chen et al.
2.3. UV–vis spectra acquisition
A UV-Vis spectrophotometer (Evolution 201, Thermofisher, Amer­
ica) was used to measure the spectra of the PE pellet extracted solutions,
and the bundled software thermo INSIGHT 2 was used for instrument
control and spectral acquisition. The spectral absorption range was set as
210–800 nm with the sampling interval of 1.0 nm. Ethanol was used as
reference blank. Finally, there were a total of 591 variables in a sample.
2.4. UPLC-Q-TOF-MS analysis
The non-volatile organic compounds migrating from virgin and
recycled PE were detected by a 1290 UPLC system coupled to 6546 Q-
TOF mass spectrometer (Agilent Technologies, Santa Clara, CA, US)
fitted with SB-C18 column (ZORBAX SB-C18, 2.1 × 100 mm, 1.8 µm;
Agilent J&W Scientific, Folsom, CA, USA), with the column temperature
of 40 ℃. The solvents used as mobile phase were water (phase A) and
acetonitrile (phase B). Mobile phase A was modified with 0.1% formic
acid for the positive ion mode. This mobile phase system was run in a
gradient elution as follows: 0–1.5 min, 5% B; 1.5–15 min, 5%–40% B;
15–25 min, 40–98% B; 25–32 min, 98% B; 32–32.1 min, 98%–5% B;
32.1–35 min, 5% B. The injection volume was 3 μL. Flow rate was 0.3
mL/min.
The parameters of mass detection were set as follows: Sensitivity
mode, capillary voltage was 4000 V, sampling cone voltage 500 V,
source temperature was 250 ℃, desolvation temperature was 300 ℃,
cone gas flow rate of was 11 L/min, the flow rate of desolvation gas was
5 L/min. The samples were analyzed in the positive ion mode and MS1
range was 50–1100 Da. MS2 analysis was performed with collision en­
ergies of 10, 20, and 40 eV, and the mass spectrometer was operated in
data-dependent acquisition (DDA) mode, with the mass range set to
20–800 Da. The software MS-DIAL version 4.38 was used for data
acquisition and processing.
2.5. Data processing and identification
UV-Vis spectrometry: the spectra were preprocessed (including
smooth, first/second derivative and the combination of the two) and
exported from thermo insight software, then the data were arranged into
a 70 (samples) × 591 (variables, i.e. transmittance at different wave­
lengths) matrix. The data matrix was imported into SIMCA 14.1 and
SPSS 20.0 for further discriminant analysis. Furthermore, the discrimi­
nation accuracy of different processing methods were compared.
UPLC-Q-TOF-MS: Peak finding, filtering and alignment were carried
out using MS-DIAL version 4.38 (http://prime.psc.riken.jp/compms/
msdial/main.html, accessed on 20/04/2021), and part of ion frag­
ments were identified by combining with the open-source metabolomics
MSP spectral kit. MS-DIAL parameters were as follows: minimum peak
height of 1000, sigma window of 0.5 and MS/MS abundance cut-off of
10 for deconvolution, and identification was done based on the open-
source MSP file score cut-off of 75%. Three types of ion adsorption
were monitored: [M+H]+, [M+NH4]+ and [M+Na]+. Variables with
more than 75% of their values as zero were removed, as they do not
possess the information to characterize the difference between two
groups (Song et al., 2021). The resulting three-dimensional matrix
containing tR, m/z and intensities of detected precursor ions was
exported to SIMCA 14.1 (Umetrics, Umeå, Sweden) and SPSS 20.0
(SPSS, Chicago, USA) for further processing.
CAS number and possible origin of all identified compounds were
retrieved from PubChem (https://pubchem.ncbi.nlm.nih.gov/, accessed
on 15/06/2021) which links to extensive databases, including “EPA
Chemical and Products Database (CPDat)”, “Hazardous Substances Data
Bank (HSDB)”, “Joint FAO/WHO Expert Committee on Food Additives
(JECFA)”, “EU Pesticides Database” and “European Medicines Agency
(EMA)”. Besides, to understand as much as possible the toxicity of these
migrants, they were then searched against EU 10/2011 regulation (EC,
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Journal of Hazardous Materials 423 (2022) 127165
2011), Chinese national standard regarding migration limits and pesti­
cide residue limits (Standardization Administration of China, 2016;
Standardization Administration of China, 2021), substances of very high
concern (SVHC) database downloaded from ECHA (https://echa.europ
a.eu/candidate-list-table, accessed on 04/06/2021) and the list of
endocrine disrupting chemicals (EDC) extracted from the UN review
report II (IPCP, 2017).
2.6. Statistical analysis
Orthogonal partial least-squares discrimination analysis (OPLS-DA)
was used to screen for the markers between recycled and virgin PE,
which was implemented in this study using SIMCA 14.1. The variable
importance in projection (VIP) was a critical metric obtained with OPLS-
DA. In general, variables with VIP greater than 1 were deemed to play
vital roles in discriminating.
Principal components analysis (PCA) is a commonly used technique
to reduce the dimensions of dataset into a few principal components
(PCs), and these PCs retain the most important information of the data.
With the help of this tool, we can visually observe the differences be­
tween samples in two or three dimensions regarding the variable in­
formation. In this study, PCA was performed using SIMCA 14.1. Log
transformation was used to highlight the importance of each variable
prior to PCA and OPLS-DA model building.
Linear discrimination analysis (LDA), a supervised learning method,
was employed to construct classification models to discriminate be­
tween recycled and virgin PE. Before the model was built, the data set
should be divided into calibration and validation set whose test accuracy
respectively represents the stability and predictability of the model. And
the LDA model was processed with SPSS 20.0.
In this case, 2/3 of the data set were used as calibration set and 1/3 as
validation set. In addition, in order to avoid the result instability caused
by manually sampling, three sampling methods (i.e. random, systematic
and stratified sampling) were used to determine the training set and
prediction set.
3. Results and discussion
3.1. The difference of UV-Vis spectrometry data between recycled and
virgin PE
The transmittance of the above 70 sample extracts was detected by
UV-Vis spectrometer. The mixture UV-Vis spectra are shown in Fig. 1a.
As we can see, the UV-Vis spectra can be roughly divided into three
regions. In the range of 510–800 nm (region I), the transmittance of both
recycled and virgin PE was nearly 100%, indicating that visual methods
could not distinguish between recycled and virgin PE. As for region II
(400–510 nm), the visible light was absorbed by many recycled PE ex­
tracts, which was the result of the extraction of the pigment from the
recycled samples. But there was no significant pattern between the two
groups in this region. In region III (210–400 nm), with the decrease of
ultraviolet wavelength, the transmittance of the extracted solution of
recycled samples decreased rapidly, while the virgin group was signifi­
cantly different from the recycled at 230–310 nm. The absorbance in the
range of 230–310 nm is associated with the n-π* electronic transitions,
due to aromatic compounds and other chromophores (hydroxyl,
carbonyl, etc.) (Rafi et al., 2018), which might be caused by the large
amount of phthalic plasticizers, antioxidants and ultraviolet absorbents
in the recycled PE (Su et al., 2021). By comparing these three regions, it
can be found that there are significant differences in transmittance be­
tween recycled and virgin group in the UV spectrum region (210–400
nm), proving UV spectrometer could be a powerful tool for discrimi­
nating recycled and virgin PE.
In this study, the data of region III was used for further PCA model
building. As shown in Fig. 1b, recycled and virgin samples formed two
main regions respectively, and the first two PCs can explain 91.8% of the
Z.-F. Chen et al.
Fig. 1. Chemometrics based on UV-Vis spectra: (a) Raw UV-Vis spectra; (b) PCA score plot based on region III (210–400 nm); (c) VIP values of different wavelengths
between recycled and virgin polyethylene; (d) PCA score plot based on marker region (237–331 nm).
total variations. The main difference between recycled and virgin group
was in the location on horizontal axis (i.e. PC1, accounting for 75.6% of
total variations). The recycled group was located on the negative half of
the horizontal axis, while all virgin samples were located on the positive
half of the horizontal axis. To further amplify the differences between
the two groups, OPLS-DA was used to filter out the weakly discrimina­
tive variables and extract markers. As we can see in Fig. 1c, the VIP
values of spectra of 237–331 nm were higher than 1, meaning that the
main difference between the two sets of data lied in this region, and the
difference between the two groups peaked at 250 nm. In PCA score plot
based on the data of 237–331 nm (Fig. 1d), the differences between the
two groups of data were more obvious, while the distribution of samples
within the group was more concentrated. Furthermore, the explanation
rate for the first two principal components was improved to 98.7%, and
PC1 (i.e. the horizontal axis) accounted for 93.1%, indicating that the
marker region can provide a set of more efficient data to discriminate
recycled and virgin PE. After variable reduction, a new matrix of 70
(samples) × 95 (variables, transmittance at 237–331 nm) was formed
and imported into the statistical software for further classification
models establishing.
3.2. Classification models based on UV data
To build classification model, data set should be split into calibration
and validation set. Calibration set was used to establish the relationships
between inputs and outputs, while validation set was applied to evaluate
the classification ability of the model (Palacios-Morillo et al., 2013).
In this study, the effect of various preprocessing methods on the
performance of LDA was compared. However, because data character­
istics of various data preprocessing methods were different, the selected
feature regions by OPLS-DA were various. For example, the marker
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Journal of Hazardous Materials 423 (2022) 127165
region of the raw data was 237–331 nm, while for the first derivative the
marker region was 227–346 nm. The results of discrimination obtained
are summarized in Table 2. As we can see, all preprocessing techniques
show a high stability and predictability, but not all of them could
improve the accuracy of distinguishing between recycled and virgin PE.
On the contrary, the fist derivative and second derivative even lowered
the discriminant ability of the model compared to raw data. The LDA
models based on both raw and smoothing data showed excellent
discriminant ability with a high accuracy of 100% in three sampling
methods. Although the model based on smoothing-second derivative
data also showed 100% accuracy, the misjudgment of second derivative
made us less trust in this result. Thus, both raw and smoothing data were
considered as the most effective and accurate data sets for the LDA
model, and UV spectrometry combined with LDA model can be a simple,
quick and accurate approach to discriminate recycled and virgin PE.
3.3. Multivariate statistical analysis based on UPLC-Q-TOF-MS data
Using the chromatographic and mass detection conditions and MS-
DIAL parameters above mentioned, 2314 ions were exported. A 70
(samples) × 2314 (variables) matrix was formed and imported into
statistical software for OPLS-DA, PCA, and LDA.
In order to filter out the common features detected by UPLC-Q-TOF-
MS and enhance the distinguishing effectiveness between recycled and
virgin PE, OPLS-DA model was established and variables with VIP
greater than 1 were reserved for further analysis. In OPLS-DA score plot,
the distance on the horizontal axis represents the difference of variables
between the two groups, while the distance on the vertical axis repre­
sents the difference within the group. As we can see in Fig. 2a, there was
a significant difference between the two groups regarding these sub­
stances detected by UPLC-Q-TOF-MS, and the differences within the
Z.-F. Chen et al. Journal of Hazardous Materials 423 (2022) 127165

Table 2
Results of the discrimination between recycled and virgin polyethylene by UV spectra combined with chemometrics.
Pretreatment Data set Sampling methods Average

Random Sampling Systematic sampling Stratified sampling

Raw Calibration (%) 100 100 100 100

Validation (%) 100 100 100 100
Smoothing Calibration (%) 100 100 100 100
Validation (%) 100 100 100 100
FD Calibration (%) 100 97.9 100 99.3 ± 1.4
Validation (%) 95.7 95.7 100 97.1 ± 2.9
SD Calibration (%) 100 100 100 100
Validation (%) 100 100 95.7 98.6 ± 2.9
Smoothing-FD Calibration (%) 100 100 100 100
Validation (%) 87.0 91.3 95.7 91.3 ± 4.4
Smoothing-SD Calibration (%) 100 100 100 100
Validation (%) 100 100 100 100

FD: first derivative; SD: second derivative.

Fig. 2. OPLS-DA based on UPLC-Q-TOF: OPLS-DA score plot based on all ions (a); permutation at 200 times (b); VIP values of all ions (c); loading scatter plot of
OPLS-DA based on high-level markers (variables with VIP > 2) (d).

recycled group were very slight, whereas the virgin group showed sig­
nificant differences and was divided into two distinct regions. The model
fit parameters were 0.530 of R2X(cum), 0.987 of R2Y(cum) and 0.975 of
Q2(cum), indicating the fitness and prediction of the OPLS-DA model. In
addition, a 200 permutation test was used to verify the model (Fig. 2b).
The intercept of R2 and Q2 regression lines was 0.477 and − 0.514
respectively, and the slope of the two regression lines was greater than 0,
proving the stability and no over-fitting of the OPLS-DA model.
In this study, variables with VIP greater than 1 were attached to great
importance in discriminating between recycled and virgin PE. Based on
this criterion, 802 variables were selected as the markers (variables with
VIP > 1). Owing to the high number of variables in the dataset, 85 high-
level markers (variables with VIP > 2) were further filtered. The final
VIP plot of OPLS-DA model is showed in Fig. 2c. In loading scatter plot of
OPLS-DA based on high-level markers (Fig. 2d), the blue squares on both
sides represent the recycled group and the virgin group, respectively.
The closer the distance between the variable (green square) and the
group (blue square), the higher the content of this variable in this group.
It can be seen that the content of all high-level markers in the recycled
group is significantly higher than that in the virgin group.
PCA is an unsupervised model which can reduce the dimensions of the
original data set. The first two PCs of PCA score plots based on all variables
(Fig. 3a), markers (Fig. 3b) and high-level markers (Fig. 3c) explained
43.0%, 67.0% and 82.9% of the original variables, respectively. The

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Z.-F. Chen et al. Journal of Hazardous Materials 423 (2022) 127165

Fig. 3. PCA score plots of recycled and virgin PE samples based on: all variables (a), markers (VIP > 1) (b) and high-level markers (VIP > 2) (c).

recycled and virgin samples formed two distinct regions in the two-
dimensional score plot. After the markers were selected, the area formed
by the two groups of samples became more concentrated and the distance
between these two groups expanded, depicting that OPLS-DA model can
be used to further amplify the differences between the two groups. The
results of PCA demonstrated that the non-volatile profiles had the poten­
tial to characterize the PE produced by different manufacturers as well as
to differentiate between recycled and virgin PE.
To build LDA model, data set was split into calibration and validation
set by the above sampling methods on the proportion of 2:1. Three LDA
models were built based on all ions, markers (VIP > 1) and high-level
markers (VIP > 2), respectively. The results are displayed in Table 3. As
can be seen, both three LDA models showed a high stability with 100%
accuracy of calibration set. The LDA model based on all ions showed a
poor prediction compared to the other two set makers, where a 75.4%
accuracy of validation set is insufficient to discriminate recycled and vir­
gin PE. As for the other two models based on markers and high-level
markers, their accuracies of validation set reach 94.2% and 97.1%, and
the later shows a smaller fluctuations. Therefore, UPLC-Q-TOF-MS showed
a powerful effect in differentiating between recycled and virgin PE.
3.4. Classification and possible origins of candidate chemicals
MS-DIAL can automatically identify the metabolite peaks by the
similarity calculation of precursor ion and MS/MS spectrum with the
reference databases. Among the 2314 features, the ions whose score
lower than 75%, or which had no MS2 information were removed.
However, there could be false positive identification in the results,
which may have a high score but the MS2 profile does not match well. As
shown in the Fig. 4a, reference compound of the peak at 17.687 min
(precursor ion is 192.1383) in UPLC-Q-TOF-MS was DEET with a high
total score of 89.5 in MS-DIAL, but the chief fragment in MS2 spectra not
matched well. Therefore, this identification was ruled out. In contrast,
although the total score of the compound in Fig. 4b was less than that of
the former, most of its fragments match the reference compound, so in
this case the result will be retained. As a result, a total of 48 candidate
compounds were successfully identified (Table 4).
The 48 candidate chemicals can be divided into 8 groups according
to their main functional groups (Fig. 5a), including ketone (31%), esters
(10%), carboxylic acid (13%), alcohols and phenols (10%), amine
(13%), nitriles (6%), aldehydes (2%) and others (15%). For the purpose

Table 3
Results of the discrimination between recycled and virgin polyethylene by UPLC-Q-TOF chemometrics.
Data set Sampling methods Average

Random Sampling Systematic sampling Stratified sampling

All features Calibration (%) 100 100 100 100

Validation (%) 69.6 78.3 78.3 75.4 ± 5.8
Markers (VIP > 1) Calibration (%) 100 100 100 100
Validation (%) 95.7 87.0 100 94.2 ± 7.2
High-level markers (VIP > 2) Calibration (%) 100 100 100 100
Validation (%) 95.7 95.7 100 97.1 ± 2.9

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Z.-F. Chen et al.
Fig. 4. Exclusion of misidentification by matching mass spectral library manually.
of understanding possible origins of those migrants, they were searched
against the above database through the website of PubChem and the
final result is shown in Table 4. Owing to these recycled PE samples were
collected from all walks of life, possible origins of the detected com­
pounds showed a wide and complex range of sources, and were even­
tually summarized into five groups: plastic, food, drug, cosmetics and
pesticide related (Fig. 5b).
The plastics-related group contains a large number of additives and
their intermediates, such as plasticizer (13.425_277.12845/Triethyl cit­
rate, 10.252_183.07806/Triethyl phosphate, 20.948_267.17358/Tributyl
phosphate, 0.798_150.11263/Triethanolamine, 0.791_106.08636/Dieth­
anolamine), slipping agent (24.741_338.3421/Erucamide, 25.218_2
82.28119/Oleamide), UV-absorber (24.214_311.16614/Avobenzone,
19.94_229.08612/Oxybenzone, 18.835_183.0807/Benzophenone), flame
retardants (18.336_327.00833/Tris(1-chloro-2-propyl) phosphate,
0.818_127.07289/Melamine), surfactant (24.058_369.38461/Tetracosa­
noic acid, 0.802_132.1019/Beta-Guanidinopropionic acid, 19.008_230.
24792/N,N-Dimethyldodecylamine N-oxide) (Xiao, 2018), etc. These
plastic additives such as plasticizers, stabilizers, antioxidants, etc, are
commonly used in many consumer products, and their association with
genotoxicity and endocrine disruption has been reported in many studies
(Das et al., 2021; Sendra et al., 2021). Moreover, many of them detected in
this study are in the EDC list and were found their SML lower than
1 mg/kg, which should be of concern. Most of these additives were
detected significantly more frequently in the recycled samples. This is
because recycled plastics need to meet the performance requirements of
the previous cycle of use, or to improve the performance of plastics after
recycling (Kazemi Najafi, 2013). Therefore, even if the pollutants adsor­
bed by recycled plastics might be cleaned thoroughly, the migration of
additives and their degradation products from recycled plastics to food is a
concern as they could accumulate during the
consumption-recovery-reconsumption cycle of plastics. Surfactants might
be added to plastics as antistatic agents, which can effectively eliminate
static electricity (Yu and Lv, 2010), but the higher average abundance of
these surfactants in recycled PE is more likely to be the residue of
decontamination process (Gecol et al., 2001). Benzaldehyde
(23.143_107.04937) was found in R4, R7, V1 and V3 samples, which could
be the residue as one of the reactants of 1,3-2,4-di(p-hydroxyl)
7
Journal of Hazardous Materials 423 (2022) 127165
benzylidene sorbitol. 1,3-2,4-di(p-hydroxyl) benzylidene sorbitol, syn­
thesized by acetal method from p-hydroxyl benzaldehyde and D-sorbitol,
is an effective nucleating agent used in polyolefin (Liu et al., 2011; Bai
et al., 2009).
As for food related (food additives or food component), they could
not raise food safety concerns but their migration might change the
original sensory properties of the contacting food (Vera et al., 2020).
Drug, cosmetics and pesticide related compounds were introduced by
the corresponding contact material that may be non-food grade. As we
can see in Table 4, all recycled PE samples had significant absorption of
food, drug or pesticide related substances during the previous cycle of
use. Pesticide ingredients could be extremely toxic, because some of
them have very low maximum residue limits for pesticides in food
(Standardization Administration of China, 2021). Therefore, if recycled
PE is going to be used as a food contact material, it needs to be insured
that the origin of recycled material is also food grade. Nine-thirteenths
of the substances with unknown possible origin were detected only in
recycled samples, most of which were probably the contaminants
introduced during the previous consumption or the recycling process.
Moreover, there are a large number of other pollutants that have not
been identified, and the chemical safety of recycled plastics needs more
research to explore.
In addition, 17 compounds with VIP bigger than 1 were also marked
in Table 4. As shown in Table 4, the average content of most markers in
the recycled group are several times than that of the virgin group,
including 3 pesticide related, 8 plastics related, 1 drug related, 1 food
related and 4 unknown source. As the examples shown in Fig. 6, most of
these marker compounds have structures such as benzene, carbonyl, and
hydroxyl that could cause n-π* electronic transitions in UV spectrom­
eter. Therefore, these markers could be the factors causing the difference
of UV spectrum between recycled and virgin group. The reason why
higher levels of some additives were detected in the recycled plastics
might be that many additives were added during mechanical extrusion
process for the purpose of mitigating the performance degradation of the
recycled plastics (Kazemi Najafi, 2013). Only in this way can recycled
plastics have better performance and longer service life in the next use
cycle. And only two ions, 0.798_150.1126 (Triethanolamine) and
24.741_338.3421 (Erucamide), show higher content in the virgin
 Table 4

Z.-F. Chen et al.

Compounds migrating from polyethylene detected by UPLC-Q-TOF.
RT_Mass Candidate name CAS Adduct Fragment ion (m/z) Score Note (SML/ADI unit: mg/kg) Samples detected
number

ketone
19.803_148.1123 3-Methyloxyindole 1504-06-9 [M+H]+ 133.0885 80.5 – R1
1.532_173.0783 1-(4-methoxyphenyl)ethanone 100-06-1 [M+Na]+ 84.9590 86.5 Food related; VIP = 2.34, R/V = 17.52 R1–R13
18.835_183.0807 Benzophenone 119-61-9 [M+H]+ 105.0333 76.2 Plastic related; SML: 0.6 (EU 2011-10) –
5.714_185.0784 Metribuzin-diketo 56507-37- [M+H]+ 157.1083 81.1 Pesticide related R1
0
15.615_192.1395 N,N-Diethyl-3-methylbenzamide 134-62-3 [M+H]+ 119.0489; 72.0811 93.3 Pesticide related R1–R11, R13
22.181_205.0865 1-[4-hydroxy-3-(3-methylbut-2-enyl)phenyl]ethanone 35816-89- [M+H]+ 149.0233 86.4 – R10, R13
8
19.240_214.1261 Octhilinone 26530-20- [M+H]+ 102.0011; 57.0698; 87.2 Pesticide related R12
1 71.0856
19.940_229.0861 Oxybenzone 131-57-7 [M+H] +
151.0386; 105.0331 91.3 Plastic related; SML (T): 6 (GB 9685-2016); EDC R1, R8–R11, R13
22.694_243.1355 Huperzine A 102518- [M+H]+ 226.1799 89.4 Drug related –
79-6
16.863_279.0933 15,16-Dihydrotanshinone I 87205-99- [M+H]+ 261.0800 83.8 Drug related R10, R11, R13
0
22.190_301.1415 [M+Na]+ 261.0800 87.3
6.722_289.1622 Dehydroepiandrosterone 53-43-0 [M+H]+ 245.0440 86.1 Drug related; VIP = 1.83, R/V = 6.07 –
24.214_311.1661 Avobenzone 70356-09- [M+H]+ 161.0952; 135.0440 92.1 Plastic related; VIP = 2.31, R/V = 46.44 R1–R13
1
22.145_361.2242 Cortisone 53-06-5 [M+H]+ 163.0704 81.7 Drug related; VIP = 1.78, R/V = 11.83 R2–R7, R9–R13
15.547_513.1367 (Z)-9-(2H-chromen-3-yl)-2-(2,3,4-trimethoxybenzylidene)-8,9- – [M+H]+ 375.1280 83.3 VIP = 1.64, R/V = 9.20 R1–R13, V1–V8
dihydro-2H-furo[2,3-f]chromene-3,7-dione
26.576_413.2667 4-(3,12,14-trihydroxy-10,13-dimethylhexadecahydro-1H-cyclopenta – [M+Na]+ 301.1400; 367.1650 83.7 – R10, R11, R13
[a]phenanthren-17-yl)furan-2(5H)-one
esters
8

18.564_194.1176 Ethyl-4-dimethylaminobenzoate 10287-53- [M+H]+ 166.0869; 134.0600; 86.4 Plastic related R6

3 179.0929
9.816_257.1361 6-ethyl-2,3,5-trimethyl-7H-furo[3,2-g]chromen-7-one 838897- [M+H]+ 144.0790 87.2 VIP = 2.06, R/V = 26.62 R1–R13
34-0
13.425_277.1285 Triethyl citrate 77-93-0 [M+H]+ 157.0495; 203.0909; 83.2 Plastic related; SML (T): 60 (GB 9685–2016); R1–R13, V1, V2,
115.0389 VIP = 1.16, R/V = 3.98 V5–V7
16.073_293.0953 Altenuene 29752-43- [M+H] +
237.1124; 265.0500; 80.6 – –
0 181.0650
19.471_415.2113 2-oxiranecarboxylate – [M+Na]+ 119.0852 81.3 – R11, R13
Carboxylic Acid
0.796_104.1074 DL-3-Aminoisobutyric acid 144-90-1 [M+H]+ 86.0964 86 – R2, R9, R12
0.802_132.1019 Beta-Guanidinopropionic acid 353-09-3 [M+H]+ 72.0566; 90.0564; 83.5 Plastic related R1–R8, R10, R13,
114.0914 V1–V8
17.586_177.0547 Protocatechuic acid 99-50-3 [M+Na]+ 149.0233 80.3 Drug related R1–R4, R7–R13

Journal of Hazardous Materials 423 (2022) 127165

24.331_179.0713 3-Methoxycinnamic acid 6099-04-3 [M+H]+ 161.0596; 133.0625; 91.5 – R1, R8–R11, R13
162.0625
0.838_215.0697 7,8-Dihydroxy-4-methylcoumarin 2107-77-9 [M+Na]+ 177.0540 87.2 Drug related R1, R3–R7
24.058_369.3846 Tetracosanoic acid 557-59-5 [M+H]+ 324.3260 88.7 Plastic related; VIP = 1.17, R/V = 11.20 R1–R13, V1–V4,
V6–V8
Alcohols and
phenols
21.114_623.3041 Tetrandrine 518-34-3 [M+H]+ 312.2956 82.4 VIP = 1.27, R/V = 5.01 R1–R13, V1–V8
0.791_106.0864 Diethanolamine 111-42-2 [M+H]+ 88.0762; 70.0647 91.8 Plastic related; SML: 0.3 (GB 9685-2016) R1–R13, V1–V8
0.798_150.1126 Triethanolamine 102-71-6 [M+H]+ 132.1018; 70.0672; 96.6 Plastic related; SML: 0.05 (GB 9685-2016); R4, V1–V8
88.0742; 114.0944 VIP = 1.74, R/V = 0.20
5.226_283.1751 Hexaethylene glycol 2615-15-8 [M+H]+ 89.0598; 133.0853; 84.3 Plastic related; VIP = 1.30, R/V = 3.76 R1–R13, V1–V8
177.1136
24.565_331.2849 Ceratodictyol – [M+H] +
93.4 –
(continued on next page)
 Table 4 (continued )

Z.-F. Chen et al.

RT_Mass Candidate name CAS Adduct Fragment ion (m/z) Score Note (SML/ADI unit: mg/kg) Samples detected
number

313.2741; 239.2366; R1, R3–R5, R10,

95.0863 R11, R13
amine
0.818_127.0729 Melamine 108-78-1 [M+H]+ 85.0509 86.1 Plastic related; SML: 2.5 (GB 9685-2016); R3, R7, R8,
VIP = 1.23, R/V = 3.91 R10–R13
0.788_134.1175 2-Aminobenzimidazole 934-32-7 [M+H]+ 90.0916; 107.0603 81.4 Pesticide related; VIP = 1.03, R/V = 2.64 R1–R3, R5, R7, R9,
R12, R13
19.008_230.2479 N,N-Dimethyldodecylamine N-oxide 1643-20-5 [M+H] +
58.0650 90.2 Plastic related; VIP = 1.02, R/V = 1.86 R1, R4–R6, R10,
R11, R13
19.791_270.1259 Acetochlor 34256-82- [M+H]+ 224.0836; 59.0489; 84.1 Pesticide related; MRL: 0.05; ADI: 0.01 (GB 2763- R1–R9, R12, R13
1 148.1122 2021)
25.218_282.2812 Oleamide 301-02-0 [M+H]+ 265.2532; 247.2432; 83.4 Plastic related; SML: 60 (GB 9685-2016) R3, R5, R9, R10,
266.2553 R13, V1
24.741_338.3421 Erucamide 112-84-5 [M+H] +
97.1007; 303.3026; 82.2 Plastic related; SML: 60 (GB 9685-2016); V2, V4, V7
21.3147 VIP = 1.32, R/V = 0.13
Aldehydes and
nitriles
23.143_107.0494 Benzaldehyde 100-52-7 [M+H]+ 79.0000 88.8 Plastic related R4, R7, V1, V3
22.038_105.0698 3-Cyanopyridine 100-54-9 [M+H]+ 77.0382; 50.9878; 88.7 Plastics related –
105.0333
17.592_150.0267 4-Hydroxymandelonitrile 13093-65- [M+H]+ 122.0970; 94.0655 81.4 – R1,R8–R10,R13
7
21.401_161.0963 2-hydroxy-6,7-dihydro-5 H-cyclopenta[b]pyridine-3-carbonitrile 108106- [M+H] +
133.0760; 106.0650 84.7 – –
97-4
others
0.905_163.1231 Nicotine 54-11-5 [M+H]+ 132.0803; 106.0000; 89.7 Pesticide related; MRL: 0.05*; ADI: 0.0008 (GB R4, R10–R12
84.0812 2763-2021)
9

10.252_183.0781 Triethyl phosphate 78-40-0 [M+H] +

98.9840; 127.0155 85.8 Plastic related; SML: 60 (GB 9685-2016) R1–R13, V1–V8
12.508_228.1296 Ametryn 834-12-8 [M+H]+ 186.0810; 91.0322 84.5 Pesticide related; MRL: 0.05; ADI: 0.072 (GB 2763- R1–R9, R13
2021); VIP = 2.06, R/V = 96.70
20.948_267.1736 Tributyl phosphate 126-73-8 [M+H]+ 98.9843; 155.0466; 85.3 Plastic related; SML: 0.05 (GB 9685-2016) R13
211.1097
21.037_305.1088 Diazinone 333-41-5 [M+H]+ 169.0794; 153.10196 83.9 Pesticide related; VIP = 1.01, R/V = 8.30 R1–R13
18.336_327.0083 Tris(1-chloro-2-propyl)phosphate 13674-84- [M+H]+ 98.9842; 174.9918 85.5 Plastic related R3
5
17.480_343.2953 Cocamidopropyl Betaine 4292-10-8 [M+H]+ 240.2325; 241.2348 86.7 Cosmetics related –

“–” in column 3 (CAS number) represents the CAS number of the candidate chemicals is not found, in column 7 (Note) represents the possible origin and toxicity of the candidate chemicals is not found, in column 8
(samples detected) represents none of samples had an average abundance of this compound more than five times that of the blank sample; In column 7 (Note): compounds with variable importance in projection (VIP)
greater than 1 were deemed to play vital roles in discriminating; “R/V” represent the average abundance ratio of the compound in recycled group to virgin group.

Journal of Hazardous Materials 423 (2022) 127165

Z.-F. Chen et al. Journal of Hazardous Materials 423 (2022) 127165

Fig. 5. Frequency distribution of candidate chemical classes (a) and their possible origins (b).

Fig. 6. The chemical structure of some marker compounds (VIP > 1) between recycled and virgin PE.

samples. The reduction of these two additives in the recycled samples
could be the result of the release to the external environment during the
previous consumption and recovery process.
4. Conclusion
As we can see, both UV-Vis spectrometry and UPLC-Q-TOF-MS
combined with chemometrics showed a high stability and predictabil­
ity to discriminate between recycled and virgin PE. UV-Vis spectra is
more accessible, simpler and faster than UPLC-Q-TOF-MS. With the help
of OPLS-DA, the marker region of the raw UV-Vis spectrum was regarded
as 237–331 nm between two groups, which should be paid close
attention during the discrimination process. Based on this region, the
accuracy of both training and prediction set could reach 100% in LDA
model. As for the classification model of UPLC-Q-TOF-MS based on high-
level markers (VIP > 2), the average accuracy of calibration and vali­
dation can reach 100% and 97.1% respectively.
In addition, UPLC-Q-TOF-MS provided plenty of ions profiling and
was used to investigate non-volatile organic compounds. By comparing
the fragment ions with reference databases using MS-DIAL, 48 candidate
chemicals were identified, including ketone, esters, carboxylic acid, al­
cohols and phenols, amine, nitriles, aldehydes and others. Their possible
origin could be classified as plastic, food, drug, cosmetics and pesticide
related. With the help of related standards and databases above, the
toxicities of 48 candidate chemicals were searched. Many of these
compounds are highly toxic, especially pesticide related, meaning that
closed loop recycling or sorting the recycled plastic articles is very
necessary. 17 of these candidate chemicals were considered as markers
(VIP > 1), and most of these markers were more abundant in recycled
PE, which might cause n-π* electronic transitions in UV spectrometer.

10
Z.-F. Chen et al.
CRediT authorship contribution statement
Zhi-Feng Chen: Conceptualization, Methodology, Software, Re­
sources, Writing – original draft. Qin-Bao Lin: Validation, Resources,
Supervision, Writing – review & editing, Funding acquisition. Ben
Dong: Methodology, Software. Huai-Ning Zhong: Resources. Zhi-Wei
Wang: Validation, Supervision.
Declaration of Competing Interest
The authors declare no competing financial interest.
Acknowledgments
This work was supported by the National Key R&D Program of China
(Grant No. 2018YFC1603204/2018YFC1603200) and National Natural
Science Foundation of China (32061160474).
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