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Comparison of Detection Methods of Microplastics in Landfill

Mineralized Refuse and Selection of Degradation Degree Indexes
Ying Zhang, Yawen Peng, Chu Peng, Ping Wang, Yuan Lu, Xiaosong He,* and Lei Wang*
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ABSTRACT: A landfill is an important sink of plastic waste and

potential sources of microplastics (MPs) when mineralized refuse
is reused. However, limitations are still present in quantifying MPs
in mineralized refuse and assessing their degradation degree. In this
study, laser direct infrared spectroscopy and liquid chromatog-
Downloaded via Luis Cumbal on October 14, 2021 at 16:51:07 (UTC).

raphy-tandem mass spectrometry (LC-MS/MS) were used to

identify MPs of mineralized refuse from a landfill. Although 25−
113 items/g MPs were detected in particles subjected to flotation,
37.9−674 μg/g polyethylene terephthalate (PET) and 0.0716−
1.01 μg/g polycarbonate (PC) were detected in the residual solids
by LC-MS/MS, indicating a great amount of plastic polymers still
presented in the residue. This suggests that the commonly used
flotation-counting method will lead to significant underestimation
of MP pollution in mineralized refuse, which might be due to the aging and aggregation process caused by the long-term landfill
process. The ratio of “bisphenol A/PC” and “plasticizer/MPs” was found to be positively correlated and negatively correlated with
the landfill age, respectively. Therefore, in addition to the spectral index such as the carbonyl index, new indexes based on the
concentrations of polymers, free monomers, and plasticizers were proposed to characterize the degradation degree of MPs in a
landfill.
KEYWORDS: laser direct infrared spectroscopy, mass spectrometry, polyethylene terephthalate (PET), polycarbonate (PC),
degradation degree, new indexes

■ INTRODUCTION
Plastics are artificial synthetic or semisynthetic organic
polymers.1 The annual global plastic production has reached
359 million tons.2 While some plastic wastes were recycled,
most plastic wastes were eventually landfilled or discarded.3 It
was estimated that approximately 6300 million tons of plastic
waste had been generated by 2015,4 of which 9% had been
recycled, 12% had been incinerated, and 79% had been
landfilled or released into the natural environment.4,5 There-
fore, a landfill is an important sink for plastics.6 Plastics in a
landfill will slowly break down into smaller particles, including
microplastics (MPs).7
After stacking in the landfill, easily degradable substances in
the waste are efficiently degraded, and the mineralized refuse
can be reused.8 In the past few decades, mineralized refuse in
landfills has been continuously exploited and applied world-
wide9 for land use, wastewater treatment, and waste gas
treatment.8,10,11 When these various sources of mineralized
refuse are reused, MPs may also re-enter the environment.
Therefore, a landfill may be a potential source of MPs.6,12,13
The numerous abundance of MPs in landfills has been
described in a few studies.6,14 For example, 20−91 items/g
MPs in landfill refuse samples of municipal solid waste from
Shanghai was reported.14 In these studies, the digestion-
flotation-microscopic counting method was commonly applied
to detect MPs, and the recovery of spiked MPs was used to
determine the reliability of the method. However, the aging
process may cause other components in landfills to adhere
closely to MPs, which decreases the recovery of the flotation
process and hinders recognition of the aged MPs, thus affecting
the reliability of the detection results. In addition, because the
fragmentation and degradation of plastics in landfills change
with the filling time, it is hard to use counting results to
evaluate the storage of MPs in landfills and compare their
abundances in different locations. The reported occurrence of
MPs in landfills (with units of items) also cannot be compared
with the production and consumption of plastics (with units of
tons). In previous work, we developed a method of alkali-
assisted thermal depolymerization coupled with liquid
Received: April 28, 2021
Revised: September 14, 2021
Accepted: September 15, 2021

© XXXX American Chemical Society https://doi.org/10.1021/acs.est.1c02772

A Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
chromatography-tandem mass spectrometry (LC-MS/MS),15
which can detect some typical MP polymers in many
environmental samples with complex matrixes, and provide
concentration values that can be compared with each
other.16−20
Spectral indexes such as the carbonyl index (CI) are often
used to evaluate the degree of MP aging.21,22 This is also a
useful tool for evaluating the degradation degree of MPs in
landfills. However, due to the significant differences of MPs in
landfills, the value of this index is closely related to the
selection of individual MP particles to be tested, and the
analysis of smaller particles is difficult due to the limited
resolution of instruments. More indexes need to be developed
to evaluate the degradation degree of MPs in landfills.
In this study, mineralized refuse and leachate samples were
collected from a landfill in China. MPs were analyzed by
stereomicroscopy and laser direct infrared (LDIR) and micro-
Fourier transform infrared (μ-FTIR) spectroscopy. In addition,
polyethylene terephthalate (PET), polycarbonate (PC), and
the free monomers p-phthalic acid (PTA) and bisphenol A
(BPA) were detected by LC-MS/MS. Fifteen phthalate ester
plasticizers were detected by gas chromatography−mass
spectrometry (GC-MS). The results of the investigation were
combined to (i) describe the abundances and distribution
characteristics of MPs in landfill mineralized refuse, (ii) discuss
the reliability of the commonly used detection method, and
(iii) screen indexes for evaluating the degree of MP aging.
■ MATERIALS AND METHODS
Chemicals and Materials. PTA was purchased from
Toronto Research Chemicals, Inc. (North York, ON, Canada).
BPA and D4-PTA (99%) were purchased from Sigma-Aldrich
(St. Louis, MO). 13C12-BPA (99%) was purchased from
Cambridge Isotope Laboratories (Andover, MA). HPLC-grade
methanol and HPLC-grade absolute ethanol (ANPEL
Laboratory Technologies Inc. Shanghai, China), 1-pentanol
(Meryer Chemical Technology Co., Ltd., Shanghai, China),
analytical-grade ZnCl2 (Damao Chemical Reagent Factory,
Tianjin, China), H2O2 (30%, Bohua Chemical Reagent
Factory, Beijing, China), and Milli-Q water were used in this
study. HLB (200 mg, 6 mL) and MCX (60 mg, 3 mL) solid-
phase extraction (SPE) cartridges were supplied by ANPEL
Laboratory Technologies Inc. (Shanghai, China).
Sample Collection. Mineralized refuse and leachate
samples were collected from a landfill located in Henan,
China, that receives approximately 160 tons of municipal solid
waste per day. The landfill is divided into four zones according
to different landfill ages, with landfill ages of 9−10 years (Zone
1), 5−6 years (Zone 2), 1−3 years (Zone 3), and <1 year
(Zone 4).
In November 2018, drilling exploration and sampling were
conducted in the landfill. A Geoprobe 7822DT, which is a
high-capacity direct push machine, was used for soil drilling
(drilling diameter: 7 cm, Geoprobe Systems Factory, USA).
Two sampling points were set up in each zone (Figure S1),
and 2−3 landfill samples were collected from each point
according to the different landfill depths. Due to the high
heterogeneity of mineralized refuse, four mineralized refuse
samples were taken from each sampling point and then mixed
as one sample. In total, there were 20 mineralized refuse
samples (Table S1).
In addition, 1−2 sampling points were set up in each zone to
take the leachate by inserting a bailer into the borehole (Figure
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S1), and 3−4 leachate samples were collected from each point
according to the different liquid level depths. Four leachate
samples were taken from each sampling point and then mixed
as one sample. In total, there were 23 leachate samples (Table
S1). All mineralized refuse and leachate samples were screened
with 2 mm stainless steel and stored at −20 °C.
Sample Pretreatment. A frequently used digestion-
flotation method with ZnCl2 solution was applied to separate
MPs (<2 mm) from mineralized refuse and the leachate.17,23,24
The details are described in the Supporting Information (Text
S1).
The suspended particles were collected with a glass fiber
filter membrane (0.45 μm). The filter membrane was placed in
a Petri dish in a fume hood and covered with aluminum foil,
and final suspected MPs were obtained after drying in a
desiccator for 2 days. After complete drying, the suspected
MPs were observed and counted under a microscope.
The fresh MP polymer (PET, PC, PE, and PP)-spiked
experiment followed the same method. One hundred particles
(<125 μm) of the fresh MPs of each polymer dyed Nile red
were accurately weighted and spiked into 1 g of mineralized
refuse in a 250 mL beaker. After fully mixing and standing for
24 h, the samples were digested and floated as described above.
Three replicates were conducted for each treatment.
PET and PC in mineralized refuse were depolymerized to
the corresponding monomers PTA and BPA according to our
previous method with minor modifications.15,16 The sieved
samples (0.5 g, <2 mm) were weighed and placed in a 100 mL
round-bottom flask, and 0.6 g of KOH and 20 mL of 1-
pentanol were added. The mixture was digested by heating at
135 °C in a stirring heating mantle for 30 min. The leachate (5
mL) was transferred to a 0.45 μm glass fiber filter membrane
through vacuum filtration, and then the suspended particles
together with the filter membrane were depolymerized in a 100
mL round-bottom flask containing 20 mL of 1-pentanol and
0.3 g of KOH. The mixture was digested by heating at 135 °C
in a stirring heating mantle for 30 min. Then, the monomers
PTA and BPA were extracted for LC-MS/MS analysis, as
described in our previous study.15 Before depolymerization,
backgrounds of the free forms PTA and BPA in solids were
extracted from the sample by the methanol/water mixture
solution (5:3, v/v) and then purified by HLB SPE cartridges
(for PTA) and MCX SPE cartridges (for BPA), respectively.
The details were shown in a previous study.18
MP Analysis. A stereomicroscope is used to describe the
quantity, size, and morphology information on MP particles,
and the detailed composition of MP polymers was identified by
LDIR. The functional groups on the surface of MPs were
detected by μ-FTIR. The mass concentrations of two typical
MPs, PET and PC, were quantified by LC-MS.
The suspected MPs on the glass fiber filter were observed
and counted using a Sunny SZN71 stereomicroscope (with a
minimum size detection limit of 20 μm) and classified into
fibers, films, granules, and fragments according to their
morphological characteristics.
The composition of MPs was identified by an LDIR
chemical imaging system (Agilent Technologies Inc., 8700
LDIR, California, USA) equipped with a quantum cascade
laser (QCL) light source and operating in reflection mode,
which can distinguish 39 kinds of plastic polymers through
database comparison. To determine the composition distribu-
tion of MP polymers in mineralized refuse, approximately 40−
50 particles of film or fiber were randomly selected from the
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mixed samples of each zone for LDIR detection. To ensure the
randomness of selection, the fibers and films were identified
one by one along a direction until the target quantity was
obtained. Each spectrum was obtained with a wavenumber
range of 975−1800 cm−1, and the sample was scanned 64
times with a resolution of 8 cm−1. The minimum detection
limit of the automatic workflow for identifying MPs was 10
μm. Agilent Clarity software with the spectrum library in the
MP test module was used for analysis of infrared spectroscopy
analysis, and the material was identified when the degree of
match with the standard spectrum was higher than 65%. The
detection of each sample was repeated three times, and the
average value was calculated.
To explore the aging trend of PE (polyethylene) in landfill
samples, μ-FTIR (Varian Technologies Inc., 610-IR California,
USA) with a mercury cadmium telluride (MCT) detector was
used in microscopic ATR mode. Ten PE films were randomly
selected from each of the 20 samples of mineralized refuse.
The samples were prepared and observed on the pressure pool
with a diamond window. Each spectrum was obtained over a
wavenumber range of 600−4000 cm−1 and scanned 128 times
with a resolution of 8 cm−1. The minimum analysis limit was
10 μm. All spectra were processed with OMNIC software, and
the data were then compared with those in databases
(Synthetic Fibers of Microscope, Hummel Polymers and
Additives, Microscope IR, Common Materials, Cross Section
Wizard) to determine the polymer type. The polymer
composition was recorded when the degree of match with
the standard spectrum was higher than 70%.
PTA and BPA were analyzed by a triple quadrupole mass
spectrometer G6460C coupled with an Agilent 1260 system
for chromatographic separation (Agilent Technologies, Inc.,
Santa Clara, CA, USA) but under different conditions. An
Ultra AQ C18 column (100 mm × 2.1 mm, 3.0 μm, Restek
Corporation, Bellefonte, PA, USA) and a Boltimate C18
column (100 mm × 3 mm, 2.7 μm, Welch Materials, Shanghai,
China) were used for chromatographic separation of PTA and
BPA, respectively.15 More detailed information on chromato-
graphic separation and the tandem MS system is contained in
Tables S2 and S3. The concentrations of PTA and BPA were
calibrated according to the corresponding internal standards
D4-PTA and 13C12-BPA. The concentrations of PET and PC
polymers in landfill samples were calculated according to eqs 1
and 2
PTA depolym × MWPTA − H2O2 /MWPTA
PETamount =
f(PTA − H O )
2 2 (1)
BPA depolym × MWBPA − 2H /MWBPA
PCamount =
f(BPA − 2H) (2)
where PTAdeploym and BPAdeploym are the masses of PTA and
BPA from the depolymerization of polymer, MW is the
molecular weight, and f is the mass percentage of PTA−H2O2
and BPA−2H in the polymer (77.4% for f PTA−H2O2, 89.5% for
f BPA−2H).
The concentrations of phthalate ester plasticizers in
mineralized refuse were detected by GC-MS with an Agilent
7890B-5977B (Agilent Technologies, Inc., Santa Clara, CA,
USA) according to EPA 8270D. Separation was achieved using
a capillary column DB-5MS (0.25 mm × 0.25 μm × 30 m,
Thermo Fisher Co., Ltd., USA) with helium (99.999% purity)
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carrier gas at a constant linear velocity of 1 mL/min. The
temperature of the injector was 250 °C, and the injection
volume was 1 μL. The GC column was programmed as
follows: the temperature was initially set at 60 °C, heated at a
constant rate of 20 °C/min up to 220 °C, and then held at 220
°C for 1 min. Finally, the column was heated at a constant rate
of 5 °C/min up to 280 °C for 3 min. The mass spectrometer
was operated in electron impact ionization mode at 70 eV with
the full scan mode and selective ion monitoring mode (SIM).
More detailed information on MS system is contained in Table
S4.
Bacterial Communities Analysis. The bacterial com-
munity of mineralized refuse samples was analyzed by Illumina
sequencing, and the details were described in the Supporting
Information (Text S2).
Quality Assurance and Quality Control (QA/QC). No
plastic tools or containers were used in the experiments except
for PP tubes. All experimental vessels were rinsed twice with
Milli-Q water and HPLC-grade methanol, dried in a fume
hood in the laboratory, and then stored in aluminum foil.
ZnCl2 solution for flotation was filtered through a 0.45 μm
polytetrafluoroethylene (PTFE) filter. The round-bottom
flasks were heated at 500 °C for 2 h in a muffle furnace
before used for depolymerization. Procedural blanks were
analyzed with every batch of 20 samples. Background
subtraction was conducted to quantify PET, PC, and phthalate
ester plasticizer concentrations and the counting of MPs by
microscopy. The depolymerization process was performed in a
fume hood to avoid external pollution by dust.
The isotope dilution method was used to calibrate the PTA
and BPA concentrations, and the recoveries in spiked
mineralized refuse were 94.8 ± 11.8% for PTA and 102.3 ±
2.1% for BPA (average ± SD). After applying to a 10:1 signal-
to-noise ratio (SNR), the limits of quantitation (LOQ) for
PTA and BPA were 0.392 and 0.034 μg/g, respectively. A
calibration standard sample was injected after every 20 samples
to check the instrument drift sensitivity, and a pure solvent was
injected into the LC-MS/MS as a check for carryover of target
chemicals from sample to sample. Standard curves ranged from
0.2−200 ng/mL for PTA and 0.2−50 ng/mL for BPA, and the
regression coefficient of the calibration curve (r) was >0.99.
For samples with concentrations above the calibration range,
extracts were diluted and reanalyzed.
Statistical Analysis. MP counting was conducted by
Capture 2.0 software (Sunny Optical Technology Co., Ltd.,
Zhejiang, China), which can also provide information on MP
size, color, and morphology. Statistical analysis was performed
using SPSS statistics 25 (IBM, NY, USA) software. The
differences among samples were tested by one-way ANOVA.
The nonparametric Kolmogorov−Smirnov test was used to
check whether the data were normally distributed. Linear
regression and Pearson correlation analysis were performed
with OriginPro 2018 software (OriginLab Corporation, MA,
USA). A p-value <0.05 was used to indicate statistical
significance.
■ RESULTS AND DISCUSSION
Occurrence of MPs in Mineralized Refuse. The number
of suspected MPs separated from the digested mineralized
refuse samples by the density flotation method ranged from 25
to 113 items/g (average: 49 ± 21 items/g). The abundance of
MPs in Zone 4 with the shortest landfill was the highest (74 ±
21 items/g), whereas the abundance of MPs in Zone 1 with
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Table 1. Composition Distribution Characteristics of Film and Fiber MPs in a Landfill Obtained by Digestion and Flotationa
landfill landfill
zone age(a) total PET PE PP PA PS PU PVC PTFE PMMA EVA N.PA C. Ru. unknown
Zone 1 9−10 50 5 16 9 0 3 4 0 2 2 1 2 4 2
Zone 2 5−6 46 5 13 7 1 0 3 3 0 0 0 2 5 5 2
filmsb
Zone 3 1−3 50 4 22 7 1 5 6 1 0 0 0 1 3 0
Zone 4 <1 50 4 16 9 0 2 5 0 3 3 1 2 3 2
Zone 1 9−10 50 7 14 3 5 0 2 2 6 4 4 1 2
Zone 2 5−6 47 7 11 4 0 0 3 3 2 2 5 2 8
fibers b
Zone 3 1−3 43 8 6 7 2 1 5 1 2 2 5 1 3
Zone 4 <1 48 5 5 4 0 2 2 0 11 3 7 0 9
Zone 1 9−10 100 12.0 30.0 12.0 5.0 3.0 6.0 2.0 8.0 2.0 1.0 6.0 8.0 3.0 2.0
proportion Zone 2 5−6 100 12.9 25.8 11.8 1.1 0.0 6.5 6.5 2.2 0.0 0.0 4.3 10.8 7.5 10.8
(%) Zone 3 1−3 100 12.9 30.1 15.1 3.2 6.5 11.8 2.2 2.2 0.0 0.0 3.2 8.6 1.1 3.2
Zone 4 <1 100 9.2 21.4 13.3 0.0 4.1 7.1 0.0 14.3 3.1 1.0 5.1 10.2 2.0 9.2
a
PP: polypropylene; PA: polyamide; PS: polystyrene; PU: polyurethane; PVC: polyvinyl chloride; PTFE: polytetrafluoroethylene; PMMA:
poly(methyl methacrylate); EVA: ethylene vinyl acetate copolymer; N.PA: natural polyamide, C.: cellulosic, Ru: rubber. bOnly films and fibers
analyzed here are due to the proportion of granules and fragments which is relatively smaller.

the longest landfill age was 38 ± 10 items/g. In comparison, in
Zone 2 (5−6 years) and Zone 3 (1−3 years), the abundance
was 41 ± 15 and 40 ± 9 items/g, respectively (Figure S2A). It
seems that the abundance of MPs in the mineralized refuse
does not increase with the landfill age, which was also found in
other studies.14 This has been explained by the increasing
plastic wastes landfilled in recent years14 and may also be due
to the aging of plastic delays their breakage.25 In addition, the
results of abundance of the aged MPs have great uncertainty
due to the uncontrollable recovery efficiency, which will be
discussed in the following paragraphs.
When the MPs were divided into four classes according to
their particle size, i.e., < 0.25 mm, 0.25−0.5 mm, 0.5−1.0 mm,
and >1 mm, the sizes of 0.5−1.0 mm (30.1%) and >1.0 mm
(31.5%) were found to be dominant (Figure S3A). There was
no significant difference in the MP sizes in the mineralized
refuse from landfill zones with different ages (p > 0.05).
However, in landfill Zone 2 with leachate recirculation, the
proportion of MPs with small particle sizes was obviously
increased, which was due to the contribution of MPs with
smaller sizes in the leachate. Fiber, film, granular, and fragment
MPs were detected in the 20 mineralized refuse samples. Fiber
was the main form of MPs, accounting for 58.9% of the total
MPs, followed by film (29.1%) and granules (7.85%) (Figure
S3B).
LDIR was used to identify the chemical compositions of the
selected MPs separated from mineralized refuse, and the
spectra of some dominant MPs are shown in Figure S4. Widely
used plastics, including polyethylene (PE), polypropylene
(PP), PET, polyurethane (PU), and polystyrene (PS), were
frequently detected in the samples. Among all the identified
MPs, the dominant component of detected MPs was PE
(21.4−30.1%), followed by PP (11.8−15.1%) and PET (9.2−
12.9%) (Table 1). The percentages of PE and PP in all
detected films were 28.0−44.0% and 14.0−18.0%, respectively,
which is due to the widespread use of PE and PP plastic bags.
The percentages of PE and PP in fibers of the mineralized
refuse were also high, up to 28.0% for PE and 16.3% for PP,
which might come from the discarded disposable plastic
products such as nonwoven masks and handbags. PET was also
abundant in mineralized refuse accounting for 10.4−18.6% of
the detected fibers and 8.0−10.9% of the detected films. It
should be noted that, as PET can be degraded to some
D https://doi.org/10.1021/acs.est.1c02772
extent,26 its surface may not be recognized due to the potential
chemical reaction. In fact, 12% of the separated fibers were
identified as “unknown”, which might be due to the aging of
polymers27 and the presence of blended materials.
LC-MS/MS has also been used to quantify the building
block monomers PET, PC, PTA, and BPA, in mineralized
refuse.28 PET and PC MPs were detected in all mineralized
refuse samples at concentrations of 72.8−1390 μg/g (average:
398 μg/g) for PET and 0.156−14.8 μg/g (average: 1.08 μg/g)
for PC (Figure 1). To the best of our knowledge, this is the
first report of the detailed mass concentration of specific MP
polymers in mineralized refuse. Among the four zones, high
PET average mass concentration of 561 μg/g was found in
Zone 2, while the PET concentration in Zones 1, 3, and 4 was
432 μg/g, 533 μg/g, and 330 μg/g, respectively. Differently,
the calculated abundance of the floated PET MPs in Zone 4
was the highest (8 items/g), whereas the abundance of MPs in
Zones 1, 2, and 3 was 5 items/g approximately (Figure S2B).
In addition to the influence of particle size distribution on mass
concentration, the huge inconsistency also indicates that there
might be large errors in the pretreatment process of flotation
separation. Besides, it should be noted that, almost no particles
matching the standard spectra by more than 65% can be
identified in the residual particles.
Mass Distribution of PET and PC MPs in the Floating
and Residual Particles. To identify the separation efficiency
of the flotation method for MPs in the mineralized refuse, PET
and PC polymers in the floating particles and the residual
particles were detected and compared with those in the
original mineralized refuse. The flotation efficiency of PET or
PC polymers (f) in mineralized refuse can be calculated
according to eq 3
C1
f=
C1 + C2 (3)
where C1 and C2 (μg/g) are the concentrations of target
polymers in the floating particles and the residual particles,
respectively.
The concentrations of PET in the floating particles were
only 28.3−197 μg/g (average: 104 μg/g). In comparison,
37.9−674 μg/g (average: 273 μg/g) PET polymer was
detected in the residual particles (Figure 2). f PET in the
mineralized refuse was 29.9 ± 9.73%, indicating that
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Figure 1. Mass concentrations of PET (A) and PC (B) MPs in
mineralized refuse of different landfill zones obtained by direct
depolymerization coupled with LC-MS/MS without digestion and
flotation.
approximately 70% of PET MPs might be undetected when the
flotation method is used.
Figure 2. Mass concentrations of PET and PC MPs in the floating particles and residual particles of mineralized refuse after the process of digestion
and flotation.
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Similarly, the amount of PC detected in the floating particles
was 0.0374−0.264 μg/g (average: 0.148 μg/g), while the
concentrations of PC (Figure 2) residual particles ranged from
0.0716 to 1.01 μg/g (average: 0.431 μg/g). f PC in the
mineralized refuse was 31.7 ± 20.2%. This confirms that
landfill MPs are difficult to separate by the flotation process.29
Several studies have found that the overall average recovery
rates for density flotation decrease with decreasing MP particle
size.30−32 However, the results of LC-MS determined indicated
that the flotation efficiency of fresh polymers (particle size less
than 125 μm) spiked in the mineralized refuse during this
process was much higher, accounting for 64.3 ± 12.1% for
PET and 56.6 ± 17.6% for PC.
In comparison, the recovery of the flotation-counting
method was also calculated by counting the abundance of
exacted MPs spiked in the mineralized refuse. The recoveries
of fresh polymers PET, PC, PP, and PE are 95.8 ± 3.5%, 88.3
± 4.7%, 95.5% ± 0.7%, and 97.0 ± 1.4%, respectively (Table
S5). The large difference in the flotation efficiency of the
freshly spiked MPs and the landfill MPs is due to the aging of
MPs in mineralized refuse. For example, some environmental
substrates, such as humic substances, exhibit strong hydro-
phobicity and stable hydrophobic structures33,34 and tend to
combine with MPs through physical adsorption during
aging;35−37 they may not be easily removed by H2O2 digestion,
thereby preventing the MPs from floating. In addition, H2O2
digestion may not eliminate interference by minerals.38−40
Therefore, the frequently used flotation method may lead to
obvious omission of MPs and result in underestimation of MP
pollution in landfills.
Spectral Index for Evaluating the Degradation of
Landfill MPs. Plastic polymers may be oxidized and
biodegraded in landfills. The degree of degradation can be
determined by infrared spectroscopy. When ATR μ-FTIR was
used to identify the change in functional groups on the surfaces
of MPs, hydroxylation (−OH: 3650−3200 cm−1, 1100−1030
cm−1) and carbonylation (CO: 1779−1680 cm−1) could be
observed on the surfaces of aged MPs. The oxidation level of
polymers can be evaluated based on the CI of the polymer
surface, which was calculated as the ratio of the absorbance
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Figure 3. FTIR spectra of reference PE and aged PE in the mineralized refuse samples with different landfill ages. The red line represents the
spectrum of the standard PE, and the black line represents the PE in mineralized refuse. PE 1#, 2#, and 3# were from Zone 1 (9−10 years), Zone 3
(1−3 years), and Zone 4 (<1 year), respectively. CI reflects the aging degree of the plastic surface. Samples of Zone 2 were not shown, because this
zone was affected by leachate recirculation.
area of carbonyl groups (between 1779 and 1680 cm−1) and
the absorbance area of the internal reference, e.g., methylene,
which are seen at 1490 and 1420 cm−1 for PE.41,42 Considering
that PE is the most commonly detected polymer in landfills,
the CI of PE could be used to assess the degree of MP
degradation in the landfill process. The CI of PE films in
landfills was much higher than that of fresh PE. There was a
significant difference (p < 0.05) in the CI of PE with different
landfill ages (Figure 3), indicating that the time spent in
landfills had a great influence on the CI. A linear correlation (r
= 0.79, p < 0.05) between the landfill age and the CI of PE in
the mineralized refuse was observed (Figure S5), indicating
that carbonylation occurs on the surface of PE during
landfilling. In addition, while CI changes sharply in the early
stage of landfills, its change slows down with the increase of
landfill age (Figure S5). This is consistent with the above
results that the abundance of MPs tends to be stable with the
waste landfill age. It is worth mentioning that the CI change
trend of PE in the leachate recirculation area (Zone 2) is
different from that in other zones (Figure S5); this might relate
to the unique distribution of microbial community in the
mineralized refuse of this zone (Figure S6).
Concentration Index for Evaluating the Degradation
of Landfill MPs. BPA, the free monomer of the PC polymer,
was detected in the mineralized refuse with a concentration
range of 0.202−3.42 μg/g (average: 1.22 μg/g, Figure S7B),
which was 1 order of magnitude lower than that of the PC
polymer. A significant positive correlation was found between
the occurrences of BPA and PC (r = 0.589, p < 0.05, see Figure
4A), which indicates the potential homology of BPA and PC.
The migration of BPA from PC plastics has been
identified,43,44 and BPA is an important degradation product
of PC polymers.45
As BPA may come from the degradation of PC, the value of
BPA/PC may reflect the degree of degradation of PC polymers
in landfills. In general, BPA/PC values showed a significant
positive correlation (r = 0.709, p < 0.01) with increasing
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landfill age (Figure 5A). High BPA/PC values of 1.69 were
observed in Zone 1, with the longest landfill age of 9−10 years.
In comparison, BPA/PC values in Zone 3 (1−3 years) and
Zone 4 (<1 year) were 1.34 and 1.06, respectively. An
exception was only found in the leachate recirculation zone
(Zone 2). A very high BPA/PC of 1.88 was found in this zone
with a landfill age of 5−6 years (Table S6). Leachate
recharging may lead to increasing BPA contamination, thus
contributing to a higher BPA/PC. Overall, BPA/PC is a
potential indicator for assessing the degree of PC degradation.
In addition, the phthalate ester plasticizers in mineralized
refuse were detected at concentrations ranging from 0.105 to
8.40 μg/g (average: 1.58 μg/g). The main plasticizers are
diisobutyl phthalate (average concentration: 2.36 μg/g) and
dibutyl phthalate (average concentration: 1.07 μg/g).
Phthalates are widely added in the manufacturing of plastic
products.46,47 Phthalates, as diesters, are easy to hydrolyze in
the environment, and the degradation cycles of phthalate
plasticizers and plastic polymers are quite different.48 There-
fore, the degree of degradation of MPs may be evaluated by the
mass ratio of plasticizer to MPs (plasticizer/MPs). The lowest
plasticizer/MP ratio of 3.04 × 10−6 was observed in Zone 1
(with the longest landfill age of 9−10 years). In comparison,
plasticizer/MP values in Zone 3 (1−3 years) and Zone 4 (<1
year) were 12.5 × 10−6 and 38.3 × 10−6, respectively (Table
S6). The value of plasticizer/MPs is negatively correlated with
landfill age (r = −0.507, p < 0.05, Figure 5B), although the
“MPs” here only contains the part of polymers that can be
separated by flotation and may contain some interfering
matrix. Therefore, plasticizer/MPs can also be used as an index
to assess the MP degradation.
As the raw material and main product of the degradation of
PET,49,50 PTA was found in all mineralized refuse samples with
a concentration range of 0.471−8.91 μg/g (average: 2.48 μg/g,
Figure S7B), which was 2 orders of magnitude lower than that
of the PET polymer. However, there was no significant
correlation between the concentrations of PET and PTA in
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
Figure 4. Relationship between typical MP monomers and polymers
in mineralized refuse. Units of PET and PTA concentrations were
represented by “ng/g” before the calculation of the natural logarithm.
The red dots were excluded as outliers, which are defined as values
that deviate from the average by more than twice the standard
residual.
mineralized refuse samples (Figure 4B). This may be due to
the very high-water solubility of PTA (Sw = 1256 mg/L
estimated from log Kow at 25 °C), which leads to its high
mobility in refuse. Furthermore, in four zones with different
landfill ages, the values of PTA/PET varied irregularly (Table
S6) and exhibited a range of 2.15 × 10−3−24.5 × 10−3.
Therefore, PTA/PET is not a suitable index to assess PET
degradation.
Distribution Characteristics of MPs in the Leachate.
Suspected MPs can be separated by flotation from all the
leachate samples (n = 23), with a count of 5−39 items/L
(Figure S8A). No regular change of MP abundance in the
leachate with landfill age was observed. This may be explained
by the varied content and composition of plastics in different
zones leading to different MPs’ release to the leachate. On the
other hand, the MPs in the leachate of a zone come from the
refuse of different landfill depths, which means the landfill age
is not exactly the same. Only in Zone 2, the abundance of
suspected MPs and PET is significantly higher (Figure S8),
which is due to leachate recirculation in this zone. The sizes of
the MPs in the leachate were much smaller than those in the
mineralized refuse samples (Figure S9). This also explains why
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Figure 5. Relationship between the potential degradation degree
indexes of “BPA/PC” (A) and “plasticizer/MPs” (B) and landfill age
of mineralized refuse. The red dots were excluded as outliers, which
are defined as values that deviate from the average by more than twice
the standard residual.
the average particle size of MPs was smaller in Zone 2, i.e., the
zone with leachate recirculation.
For the first time, high mass concentrations of PET and PC
MPs in landfill leachate were reported. PET MPs were
detected in 70.8% of the leachate samples. The detected PET
polymer concentrations ranged from 28.2 to 24100 μg/L, with
an average concentration of 5570 μg/L. PC MPs were also
detected in all of the leachate samples, with a concentration
range of 2.95−1280 μg/L (average: 178 μg/L) (Figure S7C).
The concentrations of PET and PC in the leachate are 1−2
orders of magnitude lower if compared with those in the
mineralized refuse.
In comparison, the reported PET concentrations in the
influent of WWTPs were much lower (average: 283 μg/L).20
Therefore, the input of the leachate to WWTPs will cause a
sudden increase in the load of MPs. In addition, the
recirculation of the leachate may result in the re-entry of
MPs with smaller sizes in the surface layer of the landfill, thus
increasing the risk of their transport to the atmosphere and
surrounding soil by raise dust and secondary settlement.
PTA and BPA were also detected in the leachate at
concentrations of 2.13−10300 μg/L (average: 2060 μg/L) and
0.06−44.6 μg/L (average: 24.0 μg/L), respectively (Figure
S7D). There was no significant correlation between levels of
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
monomers and polymers in the leachate, and the value of
monomer/polymer for PET or PC MPs was much higher than
that in the mineralized refuse, mainly because the soluble
monomers PTA and BPA tend to enter the leachate. In the
leachate of four zones with different landfill ages, the
monomer/polymer values also varied irregularly (Table S7)
and did not reflect the retention age of MPs in the landfill. In
addition, the interaction between other factors (e.g., landfill
age, particle sizes) on the MP distribution characteristics was
analyzed. However, although the landfill age is negatively
correlated with the concentrations of plasticizers and PTA, no
significant correlation between them was found (Figure S10).
The Storage of Typical MPs in Mineralized Refuse
and Its Release Risk. The storage of these MPs (F1, tons) in
landfills can be calculated as in eq 4, based on the mass
concentrations of PET and PC in the mineralized refuse
F1 = CMPs × m × 10−6 (4)
where CMPs is the average concentration of MPs in the
mineralized refuse (μg/g), and m is the mineralized refuse
amount (tons). When the average concentrations of PET (398
μg/g) and PC (1.08 μg/g) were substituted, the result
indicated that there might be 37 tons of PET MPs and 0.1 tons
of PC MPs in this landfill.
With the continuous generation of waste, the landfill waste
needs to be excavated and screened, and the mineralized refuse
reused. After composting and fermentation, excavated
mineralized refuse can be used as daily cover material,
nutrimental soil, processed construction material, and packing
material for biofilters used to effectively treat various
wastewaters.8,10 Mineralized refuse contains a very high
concentration of MPs, which may be an important source of
environmental MP pollution. As the ecological effects of MPs
are constantly discovered,51,52 it is of great significance to
evaluate the risk of MP release caused by the reuse of
mineralized refuse.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.est.1c02772.
Text S1, detail procedure of mineralized refuse sample
pretreatment; Text S2, methods of microbial diversity
analysis; Table S1, information of mineralized refuse and
leachate sample collection in target landfill; Tables S2−
S4, instrument performance and MS/MS parameters;
Table S5, flotation efficiency of fresh polymers spiked in
mineralized refuse; Tables S6 and S7, potential
concentration index for evaluating degradation degree
of landfill MPs in mineralized refuse and leachate from
different zones, respectively; Figure S1, layout of
sampling points; Figure S2, abundance of suspected
MP (A) and PET polymers (B) in mineralized refuse;
Figure S3, size distribution (A) and morphology (B) of
MPs in mineralized refuse obtained by digestion and
salinity flotation; Figure S4, infrared spectra of main
MPs in fibers and films; Figure S5, relationship between
CI of PE in mineralized refuse of different zones and the
corresponding landfill age; Figure S6, PCoA plots of
bacterial community structure in four landfill zones;
Figure S7, concentration of MP polymers and
monomers in mineralized refuse and leachate; Figure
H https://doi.org/10.1021/acs.est.1c02772
pubs.acs.org/est Article
S8, abundance of suspected MP (A) and PET polymers
(B) in leachate; Figure S9, size distribution of suspected
MPs in leachate; Figure S10, RDA analysis between
environmental factors and MP characteristics (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Lei Wang − MOE Key Laboratory of Pollution Processes and
Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China; orcid.org/0000-0002-8193-
9954; Email: wang2007@nankai.edu.cn
Xiaosong He − State Key Laboratory of Environmental
Criteria and Risk Assessment and State Environmental
Protection Key Laboratory of Simulation and Control of
Groundwater Pollution, Chinese Research Academy of
Environmental Sciences, Beijing 100012, China;
orcid.org/0000-0001-7447-4848; Email: hexs82@
126.com
Authors
Ying Zhang − MOE Key Laboratory of Pollution Processes
and Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China
Yawen Peng − MOE Key Laboratory of Pollution Processes
and Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China
Chu Peng − MOE Key Laboratory of Pollution Processes and
Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China
Ping Wang − MOE Key Laboratory of Pollution Processes and
Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China
Yuan Lu − MOE Key Laboratory of Pollution Processes and
Environmental Criteria/Tianjin Key Laboratory of
Environmental Remediation and Pollution Control, College of
Environmental Science and Engineering, Nankai University,
Tianjin 300350, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.1c02772
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Key Research and
Development Project of China (2018YFC1800702,
2018YFC1800703, and 2018YFC1901401) and the National
Natural Science Foundation of China (41722304 and
42077336). The study was also funded in part by the National
Natural Science Foundation of China (21777075 and
41773109), Tianjin Municipal Science and Technology Bureau
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
(18JCJQJC47100), and the Ministry of Education, China
(T2017002).
■
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