Article 1

Sorption behavior of organic pollutants on biodegradable and 2

nondegradable microplastics: pH effect 3

Maja Vujić1*, Sanja Vasiljević1, Jasmina Nikić1, Branko Kordić1, Jasmina Agbaba1, Aleksandra Tubić1 4

1 University of Novi Sad Faculty of Sciences, Department of Chemistry, Biochemistry and Environmental 5
Protection, Trg Dositeja Obradovića 3, 21000 Novi Sad, Republic of Serbia; maja.loncarski@dh.uns.ac.rs 6
* Correspondence: maja.loncarski@dh.uns.ac.rs; Tel.: +381-21-485-2798 7

Abstract: Microplastics (MPs), chlorinated phenols (CPs), polycyclic aromatic hydrocarbons (PAHs) 8
and halogenated benzenes are pollutants that are widely present in freshwater systems. As alterna- 9
tives to conventional plastics, bioplastics are receiving a lot of attention, but there is limited data on 10
their impact on pollutants' behavior. This work therefore investigates pH impact on the sorption of 11
CPs, PAHs and halogenated benzenes on seven different plastics using kinetics and isotherm stud- 12
ies. The pH of water matrix has impacted the adsorption behavior of CPs on all selected types of 13
MPs, with the highest degree of adsorption occurring at pH 7 for majority of selected CPs. On the 14
other hand, the pH value of the water matrix does not affect the adsorption of halogenated benzenes 15
and PAHs on MPs. The pseudo-second order rate model fitted the adsorption kinetics data of all 16
experiments. The results obtained for the adsorption of chlorinated phenols on microplastics indi- 17
cated a lower sorption affinity of chlorinated phenols with microplastics particles at pH 4 and pH 18
10 compared to pH 7. The Langmuir isotherm, at pH 7, implied that 4-chlorophenol’s adsorption 19
affinity was not significantly influenced by the type of plastic. On the other hand, at pH 7, the ad- 20
sorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol varied greatly, with 21
powdered types of microplastics showing the highest affinity for CPs adsorption. 22

Keywords: microplastics, biodegradable plastic, chlorinated phenols, halogenated benzenes, poly- 23

cyclic aromatic hydrocarbons, adsorption, pH effect 24
25

1. Introduction 26
Wide usage of plastic and poor management of plastic wastes presents now one of 27
the main trets to the environment and all the living society has faced a worldwide plastic 28
Citation: To be added by editorial
pollution crisis due to its massive usage and [1]. Needless to say, reports of concerning 29
staff during production.
plastic pollution are available since the ‘70s, however, scientific community has grown 30
Academic Editor: Firstname Last- interest in this topic at the start of the 21st century, making the presence of microscopic 31
name plastic particles in the environment a relatively recent area of research [2,3]. Based on the 32
latest report by Plastic Europe, in 2021 global plastic production increased by 4% which 33
Received: date
Revised: date
is more than 390 million tonnes implying it’s still urging need on the market [4]. 34

Accepted: date
The wide application of plastics in industry, transport, medicine, commercial and 35
Published: date household activities, as well as poor management of plastic waste, has led to the fact that 36
the residues after the degradation of these materials, better known as micro- and nano- 37
plastics, have become one of the emerging contaminants in the environment [1–3]. In ad- 38

Copyright: © 2023 by the authors.

dition to the decision-makers to limit the use of plastic in everyday human activities, as 39

Submitted for possible open access

well as the efforts of the scientific and professional communities to find optimal solutions 40

publication under the terms and for reducing pollution, as well as suitable substitutes for plastic materials, several hun- 41
conditions of the Creative Commons dred million tons of plastic products are still produced every year [4]. 42
Attribution (CC BY) license
(https://creativecommons.org/license
s/by/4.0/).

Appl. Sci. 2023, 13, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/applsci

Appl. Sci. 2023, 13, x FOR PEER REVIEW 2 of 14

There are many different types of plastics present in the environment, but the most 43
frequently detected are polypropylene (PP), low density polyethylene (LDPE), high den- 44
sity polyethylene (HDPE), polyvinyl chloride (PVC), polyethylene terephthalate (PET) 45
and polystyrene (PS). These types of plastics, along with numerous other kinds, come in 46
various sizes, shapes, colours, and in commercial usage typically further treated with ad- 47
ditives (e.g. fillers, plasticizers, stabilizers) to modify their properties. Different sizes of 48
plastic particles are present in the environments due to the fragmentation of plastic mate- 49
rials under the mechanical abrasion, ultraviolet radiation, thermal oxidation, and biodeg- 50
radation and ones that are in range between 1 and 1000 μm are classified as microplas- 51
tics (MPs) [5–8]. Due to the widespread of plastic pollution, and therefore MPs have been 52
detected laboriously throughout all environments [9]. Due to the MPs different shape and 53
size occurrence in the environment these particles have different environmental fates, bi- 54
oaccumulation, and effects on living organisms. Additionally, MPs contamination 55
throughout the natural environment has unavoidably led to its exposure within the hu- 56
man body which is why, in the main, it is important to understand what consequences 57
occur due to its exposure. 58
The research carried out so far, all over the world, has shown that in all parts of the 59
environment, you can find remains of plastic which size fall between 1 and 1000 μm, 60
which in recent times is most often used as the definition of microplastics (MPs). The range 61
of polymers that are included in this group is very wide, and the effects of polypropylene, 62
polyethylene, polyvinyl chloride, polyethylene terephthalate and polystyrene on the en- 63
vironment and the living world in different media are most often investigated [5–8]. De- 64
tected microplastic particles are of different shapes and sizes, colors and densities, as well 65
as other characteristics, depending on their origin in the environment, age, as well as the 66
process they went through during plastic production, application, and the environmental 67
conditions in which they occurred. Any change in the basic polymer during production 68
(addition of additives, plasticizers, etc.), as well as during lifetime in the environment, will 69
affect the properties and behavior of MPs in the environment, their interaction with other 70
compounds (e.g. organic and inorganic pollutants, etc.), as well as their potential harmful 71
impact on living organisms and human health [5,6,9]. 72
From the environment, MPs can sorb and accrue organic pollutants and heavy met- 73
als due to their hydrophobic properties and expressly, large surface areas[10–13]. Beside 74
MPs properties and the concentration, there are other factors, shown in Figure 1., influ- 75
encing sorption capacity of pollutants such as temperature, pH, ionic strength, dissolved 76
organic matter content, solubility, concentration of pollutant and many other [13,14]. 77

78
Figure 1. Most important factors influencing the sorption of 79
pollutants on microplastics 80
81
Appl. Sci. 2023, 13, x FOR PEER REVIEW 3 of 14

In terms of different factors influencing sorption of pollutants, pH has been high- 82

lighted as the most significant, since in many cases it can affect both the sorbent surface 83
properties and the nature of the sorbate. Several studies emphasized the impact of pH, as 84
an environmental factor, implying increase or inhibition of the adsorption capacity de- 85
pending on the polymer type as well as type of pollution [15,16]. In that regard, previous 86
research results implied that the surface of polyethylene and polystyrene particles 87
changes, protonates, with the decrease of pH, consequently increasing the sorption of or- 88
ganic pollutants, like perfluorooctane sulfonate, chlorinated phenols etc. [3,17–19]. More- 89
over, variable pH of the surrounding water may change the ionization states of pollutants 90
and influence their sorption processes on MPs [3,17–19] . Among the number of researches 91
investigating the adsorption of various organic pollutants (like pesticides, or pharmaceu- 92
ticals) on number of MPs [19–31], pH is not always considered. However, as one of the 93
main factors, the influence of pH on the sorption behavior of MPs has not yet been fully 94
understood and should be investigated further. Specifically, the amount of information 95
available about how pH affects the adsorption mechanism of organic pollutants is limited. 96
Additionally, usually studies have only concerned the sorption interactions between 97
MPs and single-solute systems, often neglecting the fact that mixtures of pollutants are 98
more common in natural environments. The behavior of organic pollutants in mixtures 99
can be very different compared to single compound system and highly complex sorption 100
interactions can occur with the adsorbent such as MPs. Thus, only studying the sorption 101
process in single-solute systems may not be enough for predicting the interaction between 102
organic pollutants and MPs in the water environments [15,32–34] . 103
Based on previous discussion and our earlier studies, we hypothesized that various 104
MPs have different sorption capacity for specific groups of organic pollutants, and due to 105
its different phisico-chemical characteristics the sorption behavior of chlorinated phenols 106
-CPs, polycyclic aromatic hydrocarbons – PAHs and halogenated benzenes on the MPs 107
can be influenced by environmental factors. Therefore, the main objective of this study 108
was to investigate influence of one of the most important environmental factors, pH value, 109
on the adsorption behaviors and mechanisms of CPs, PAHs, and halogenated benzenes 110
on seven types of microplastics, which are frequently detected in water environment. 111

2. Materials and Methods 112

2.1. Materials 113
In this study, MPs selected as a sorbents for the experiments are: commercially avail- 114
able powdered polyethylene standard (PEp, supplied by Thermo Fisher Scientific), gran- 115
ulated polyethylene standard (Peg, supplied by Sigma-Aldrich), polyethylene tereph- 116
thalate standard (PET, supplied by Sigma-Aldrich) and polypropylene standard (PP, sup- 117
plied by Sigma-Aldrich); two types of powdered polyethylene isolated from different per- 118
sonal care products (PE_PCPs_1 and PE_PCPs_2) and one biodegradable microplastic, 119
polylactic acid (PLA, supplied by Sigma-Aldrich). Isolation of MPs from personal care 120
products was conducted by using isolation method provided by Lončarski et al. (2020), 121
including mixing of the product with boiled water (100 ˚C) and addition of 30% H2O2 for 122
organic matter degradation [19,29]. 123
In order to better understand adsorption behavior of selected organic pollutants on 124
microplastic, characterization of selected MPs was conducted. Chemical characterization 125
of selected commercially available MPs, PLA and particles isolated from personal care 126
products was conducted by Fourier transform infrared spectroscopy (FTIR) (Thermo-Ni- 127
colet Nexus 670 FTIR spectrometer, Thermo Fisher Scientific, USA) and the conducted 128
results are presented in Figure A1. The obtained results of FTIR analysis were compared 129
with the OMNIC software Library, which confirmed the chemical structure of all selected 130
polymers. More details about chemical characterization of PEp, PE_PCPs_1, PE_PCPs_2, 131
PEg, PET, PP and PLA are given in Lončarski et al. (2020, 2021). Physico-chemical prop- 132
erties of investigated MPs attained by Brunner Emmett Teller (BET) analysis are presented 133
in Supplementary material (Table A1). The size of the granulated types of selected micro- 134
plastics (PEg, PET, PP and PLA) were provided by the supplier and it was 3 mm [19,20,29]. 135
Appl. Sci. 2023, 13, x FOR PEER REVIEW 4 of 14

The sizes of used powdered MPs (Figure A2) were achieved by scanning electron micro- 136
scope (TM3030, Hitachi, Japan) and it ranged between 49.7 to 259 µ m for the PEp particles 137
and 80-358 µ m for PE isolated from the two personal care products [35]. Additionally, the 138
determination of the point of zero charge (pHPZC) was performed according to the proce- 139
dure by Ofomaja and Ho (2008). Detailed procedure of determination of point of zero 140
charge is given in Appendix A [36]. 141
Halogenated benzenes (1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlo- 142
robenzene, pentachlorobenzene, hexachlorobenzene and trifluralin), chlorinated phenols 143
(4-chlorophenol, 2,4- dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol) and 144
polycyclic aromatic hydrocarbons (naphthalene, fluorene, fluoranthene and pyrene) man- 145
ufactured by Pestanal® , were selected as a sorbate model and their physico-chemical char- 146
acteristics are presented in Table A2. The selected organic pollutants differ in hydropho- 147
bicity and water solubility, suggesting that their behavior in the presence of MPs in water 148
would also be different. Additionally, physico-chemical characteristics of the synthetic 149
water used in paper are given in Tubić et al. (2019) and presented in Appendix A (Table 150
A3) [20]. 151
Hexane (J.T. Baker), methanol (J.T. Baker), acetic anhydride (Sigma-Aldrich) and hy- 152
drogen peroxide (Sigma-Aldrich) were used in the experiments. CaCl2 (Sigma-Aldrich), 153
NaHCO3 (Sigma-Aldrich) and MgSO4·7H2O (Sigma-Aldrich) were used for preparation of 154
the synthetic water matrix, while HNO3 (Fluka) and NaOH (Sigma-Aldrich) were used to 155
adjust the pH value of the water. All the reagents were analytical grade without further 156
purification. 157

2.3. Batch adsorption experiments 158

Sorption experiments of adsorption kinetics and adsorption mechanisms of selected 159
organic pollutants on various types of MPs were conducted using a batch equilibrium 160
method in laboratory conditions. The adsorption kinetic models were applied to deter- 161
mine the relationship between adsorption time and adsorption capacity, as well as to an- 162
alyze selected organic pollutants’ adsorption mechanism on MPs. The pseudo-first order 163
kinetic, pseudo second-order kinetic and Elovich models were used in this study. The ad- 164
sorption kinetic procedure are presented in our previous papers by Tubić et al. (2019, 165
2021) and Lončarski et al. (2021) and described in Appendix A [19,20,35]. In order to de- 166
termine the adsorption mechanism of organic pollutants on MPs adsorption isotherms 167
experiments were performed. Detailed experiment procedure is given in Tubić et al. (2019, 168
2021) and Lončarski et al. (2021) papers and presented in Appendix A [19,20,35]. 169

2.4. Analytical procedure, quality assurance and quality control 170

The pH value of aqueous samples was measured using an instrument 340i, WTW, 171
SenTix® 21 electrode, according to the method of SRPS H.Zi.111:1987. Determination of 172
DOC was performed by LiquiTOC II (Elementar, Germany), according to the method 173
SRPS ISO 8245:2007. Determination of chloride concentration in water was performed ac- 174
cording to the method SRPS ISO 9297/1:2007. Determination of sulfate concentration was 175
performed by iodometric titration of excess chromate ion with sodium thiosulfate solution 176
after sulfate precipitation by addition of excess barium chromate. Determination of water 177
alkalinity, in a form of hydrogen carbonate concentration, was performed by volumetric 178
method (APHA, 1982). Determination of selected organic pollutants was performed using 179
a gas chromatography with a mass detector (Agilent 7890A/5975C, GC/MSD) and gas 180
chromatograph with electron capture detector (GC/μECD). Detailed analytical procedure, 181
quality assurance and quality control are given in our previous papers and shown in Ap- 182
pendix A [19,20,29,35]. 183
184
Appl. Sci. 2023, 13, x FOR PEER REVIEW 5 of 14

3. Results and Discussion 185

3.1. Determination of point of zero charge 186
Point of zero charge (pHPZC) indicates the pH value at which the surface of the mate- 187
rial is neutrally charged. The point of zero charge is an important parameter for explaining 188
the adsorption behavior of the sorbent, in this case microplastics. In order to assay the 189
possible influence of the constituents of the water matrix on the pHPZC the experiments 190
were conducted in both distilled water and a synthetic water matrix. 191
Obtained results for determination of pHPZC for selected types of microplastics in 192
distilled water and synthetic water matrix are shown in Figure A3. The point of zero 193
charge obtained forselected types of MPs in distilled water ranged from pH=3.83 - 8.17 in 194
the following order: PP< PLA<PET<PEp<PEg<PE_PCPs_2<PE_PCPs_1. Furthermore, the 195
point of zero charge obtained for MPs in the synthetic water matrix was in the range from 196
pH=4.04 to pH=8.71, with the sequence PP<PLA<PET<PEg<PE_PCPs_2< PEp<PE_PCPs_1. 197
Based on the obtained results shown in Figure A3, the constituents of the water matrix 198
don’t have any effect on pHPZC for the selected types of MPs, except in the case of PEp 199
where the pHPZC in distilled water was pHPZC =4.70 while in the synthetic matrix it was 200
pHPZC =8.21. 201
Xu et al. (2018) also determined the point of zero charge of polyethylene, where its 202
obtained value in distilled water was pHPZC =4.30. The results obtained by Xu et al. (2018) 203
also indicated that the constituents of the water matrix significantly affect the charge of 204
microplastics [37]. Additionally, research by Fotopoulou and Karapanagioti (2012) indi- 205
cated that the water matrix has a significant effect on the point of zero charge of the ma- 206
terial [38]. On the other hand, based on the obtained results of the point of zero charge for 207
powdered polyethylene isolated from cosmetic products (PE_PCPs_1 and PE_PCPs_2), it 208
can be observed that the change of the water matrix has lower effect on these materials in 209
comparison with PEp. Furthermore, the pH value at which PE_PCPs_1 and PE_PCPs_2 210
are neutrally charged in distilled water is lower, pHPZC=8.11 and pHPZC=6.14, compared to 211
the synthetic water matrix, pHPZC=8.71 and pHPZC=7.29, respectively. This behavior of iso- 212
lated microplastics in relation to pure PEp can be explained by the change in the structure 213
of polyethylene during the production process of cosmetic products, which possibly sta- 214
bilizes the surface of the polymer and significantly reduces the influence of the water ma- 215
trix on the change in the point of zero charge of PE_PCPs_1 and PE_PCPs_2 [39]. A con- 216
sequence of the production of personal care products can also be a reason of a significant 217
difference in surface charge between isolated microplastic particles (pH PZC =8.11 and 6.14 218
for PE_PCPs_1 and PE_PCPs_2, respectively) and PEp (pH PZC =4.70) in distilled water. 219
pHPZC values obtained for PEg, PET, and PP in distilled water were 5.06, 4.66, and 220
3.83, respectively, which is in accordance with the results of other authors [18,40]. By com- 221
paring the obtained results of the point of zero charge of granular types of microplastics 222
in distilled water and synthetic matrix with other powdered types of microplastics, it can 223
be noted that in the case of granular microplastics (PEg, PET, PP), the influence of the 224
water matrix on pHPZC is significantly smaller. This behavior can be attributed to the 225
greater granulation and smooth surface of microplastics, where the presence of salt in the 226
synthetic matrix could not affect the change in pH PZC [38,41–44]. 227
Different surface charges of selected types of microplastics depending on the pH 228
value and chemical composition of the water matrix can lead to their different behavior 229
in the environment [38]. The obtained results shown in Figure A3 imply that that at pH 230
7.23±0.06 for the synthetic the surfaces of pure PEp, as well as PE_PCPs_1 and PE_PCPs_2, 231
will be positively charged (pH< pHPZC). On the other hand, pHPZC for PP, PET, PLA and 232
PEg (pHPZC = 4.04; 4.53; 5.28 and 5.90, respectively) indicates that at the pH of the synthetic 233
water matrix, their surfaces will be negatively charged. 234
235
Appl. Sci. 2023, 13, x FOR PEER REVIEW 6 of 14

3.2. pH effect on sorption affinity of organic pollutants on MPs 236

In this study, the adsorption behavior of selected three groups of organic pollutants 237
on MPs was obtained at three different pH values (pH 4, 7 and 10) in order to cover the 238
widest range of pH values in water environment possible. Figures A4-6 shows that change 239
of pH value of water matrix has the highest impact in case of selected CPs. On the other 240
hand, change of pH value has very low impact on adsorption behavior of selected PAHs 241
and halogenated benzenes on MPs. 242
Obtained results shown in Figure A6, imply that the highest percentage of adsorption 243
of CPs is observed at pH 7 (25 to 68%). The adsorbed percentage of 4-CP adsorbed on MPs 244
was in the following order PP (30%) < PE_PCPs_1 ≈ PE_PCPs_2 ≈ PLA (35-40%) < Pep ≈ 245
PEg (48%) < PET (60%). Furthermore, the results imply increasing of adsorption percent- 246
age of 2,4-DCP onto MPs and the the adsorption percentage increase as follows 247
PE_PCPs_1 (40%) < PE_PCPs_2 ≈ PEg ≈ PLA (50%) < Pep ≈ PET ≈ PP (65%). The adsorption 248
affinity of 2,4,6-TCP and PCP on MPs was the highest in the terms of PP, PLA, PE_PCPs_2 249
and PEg (around 50-60%). A slightly lower adsorption percentage has been determinated 250
for of 2,4,6-TCP and PCP on PEp and PE_PCPs_1 (30-40%), while the lowest is found with 251
PET, at 25-30%. 252
Based on the physico-chemical characteristics of CPs shown in Table A2, to be pre- 253
cise, pKa values of the acid constants, it can be seen that at pH 4 the selected chlorinated 254
phenols used in this study will be in molecular form, while at pH 10 they will be in its 255
ionic form. Additionally, based on the experimentally determined pHPZC microplastics at 256
pH 4 all selected microplastic particles (PEp, PE_PCPs_1, PE_PCPs_2, PEg, PET, PP and 257
PLA) are positively charged, while at pH 10 their surfaces are negatively charged. There- 258
fore, at pH 4 of water, the binding percentage is low due to the inability to form interac- 259
tions between the positively charged surface of microplastics and chlorinated phenols in 260
molecular form [45,46]. On the other hand, at pH 10, the surface of microplastics is nega- 261
tively charged, and the investigated chlorinated phenols are in ionic, negatively charged, 262
form. Knowing that fact, at pH 10 selected CPs are repelled from the surface of MPs and 263
a low percentage of interactions are formed in comparison to pH 7 [45,46]. 264
Based on the obtained results, a slight influence of the pH value on the formation of 265
interactions between the tested benzene derivatives and microplastics can be observed. It 266
is also possible to observe a significantly higher binding percentage compared to the re- 267
sults obtained for chlorinated phenols (Figure A4-5). This behavior can be explained by 268
the higher hydrophobicity of the selected benzene derivatives compared to chlorinated 269
phenols, and therefore by the greater tendency towards adsorption on microplastics 270
[47,48]. Based on the results shown in Figure A5 the selected halogenated benzenes have 271
the highest adsorption affinity towered the PE standard and those isolated from cosmetic 272
preparations, PE_PCPs_1 and PE_PCPs_2. Additionally, an increase in the binding per- 273
centage with MPs halogenated benzenes showed with an increase in hydrophobicity in 274
the range of 55-99%. Thus, the binding percentage of halogenated benzenes changes in the 275
following order: 1,2,3-TeCB<1,3,5-TeCB<1,2,4-TeCB<PeCB<HeCB<TFL. The results shown 276
in Figure A5 imply that selected halogenated benzenes have a significantly lower affinity 277
for PLA (30-90%) in comparison to the selected nondegradable types of MPs. Similar re- 278
sults were obtained in terms of the influence of the pH value on adsorption of PAH on 279
MPs. Based on the results shown in Figure A6, an insignificant influence of the pH value 280
on the formation of interactions between selected PAHs and MPs can be observed. Addi- 281
tionally, obtained results imply slightly higher affinity of naphthalene and fluorene tow- 282
ered the standard of polyethylene (both PEp and PEg), PE_PCPs_2 compared to other 283
types of microplastics which can be consequence of its larger specific surface area of PEp, 284
PEg and PE isolated from cosmetic in comparison to the active surface area of the other 285
selected types of MPs. Obtained results shown in Figure A6 imply that adsorption affinity 286
of selected PAHs towered MPs increase with its hydrophobicity, and the difference in the 287
binding percentage on microplastics is less significant. Thus, naphthalene, which is less 288
hydrophobic, has the lowest affinity towards MPs. The percentage of naphthalene adsorp- 289
tion was about 20% for PET, while for PEp, PEg, PE_PCPs_1, PE_PCPs_2 and PP it was 290
Appl. Sci. 2023, 13, x FOR PEER REVIEW 7 of 14

about 85%, 95%, 65%, 95% and 75%, respectively. With the increase in the hydrophobicity 291
of the tested PAHs, an increase in the binding percentage was determined, in the case of 292
all four types of PE and PP, it was in the range of 95-99%, while for PET it was 65%. The 293
lowest adsorption affinity of PAHs was shown to PLA where the binding percentage for 294
naphthalene, fluorene, fluoranthene and pyrene was 30%, 50%, 60% and 75%, respec- 295
tively. 296
Since the change of pH value had the highest impact on adsorption behavior of CPs 297
towards MPs, in order to better understand pH effect on its sorption kinetics on MPs the 298
obtained experimental data were fitted with three kinetic models: the pseudo-first order, 299
pseudo-second order and Elovich model. Furthermore, to better understand the influence 300
of pH value defer on adsorption mechanism of selected CPs on MPs, the adsorption iso- 301
therm experiments were conducted. 302

3.3. The pH effect on adsorption kinetics of chlorinated phenols on MPs 303

The results of the sorption kinetics of CPs on the PEp, PE_PCPs_1, PE_PCPs_2, PEg, 304
PET, PP and PLA particles in different pH of water matrix are shown in Figure 2. The 305
adsorption of selected CPs onto MPs reached equilibrium after 12-48 h depending on the 306
sorbate–sorbent combinations investigated. As shown in Figure 2, the uptake of CPs by 307
the selected types of microplastics and bioplastic-PLA increases with time until sorption 308
equilibrium is achieved after 12h in case of powdered MPs and 48 h for granulated MPs. 309
These results are in the range of the usually reported periods for gaining sorption equilib- 310
rium of the organic compounds on various types of MPs. 311
Powdered types of MPs have the highest uptake for all selected CPs at neutral pH, 312
pH 7 and the highest adsorption affinity at pH 7 was obtained for 2,4-DCP, 221.0 µ g/g. 313
The other three selected CPs indicated lower adsorption affinity compared to 2,4-DCP, 314
137.7 µ g/g, 162.0 µ g/g and 90.74 µ g/g for 4-CP, 2,4,6-TCP and PCP, respectively. A smaller 315
adsorption affinity towered this type of MPs can be consequence of both the physico- 316
chemical properties of the compound and the molecular structure. Based on the physico- 317
chemical properties of the selected CPs, shown in Table A2, it can be assumed that PCP 318
will exhibit the greatest change in the adsorbed amount on PEp, due to its low solubility 319
in water and the highest hydrophobicity compared to the other tested chlorinated phe- 320
nols. The influence of the hydrophobicity of molecules on the adsorption of organic com- 321
pounds on microplastics was pointed out by Wang and Wang (2018), who concluded that 322
compounds with higher hydrophobicity are better adsorbed on microplastics. However, 323
the amount of PCP adsorbed is the smallest, which can be a consequence of the size of the 324
molecule and the position of chlorine atoms in the PCP molecule, which hinder the ap- 325
proach of the hydroxyl group to the surface of PEp, and thus its adsorption. Furthermore, 326
this confirms the chemical structure of 2,4-DCP and 2,4,6-TCP, where with the decrease 327
in the number of chlorine atoms, the adsorption affinity increases (qt=221 µ g/g for 2,4- 328
DCP and qt=162.0 µ g/g for 2,4,6-TCP) [18,49]. 329
On the other hand, the obtained results shown in Figure 2 indicate that at pH 4, the 330
adsorption affinity of all selected CPs towards MPs decreases in comparison with data 331
attained at pH 7. It also implies that regardless of pH change, the highest adsorption af- 332
finity of CPs was obtained for powdered types of MPs. Additionally, at pH4, the highest 333
adsorbed amount was attained for 2,4-DCP on polyethylene isolated from personal care 334
products (73.8-91.0 µ g/g). Same as in case of pH 7, at lower pH of water matrix (pH 4) the 335
adsorbed amount of CPs with higher hydrophobicity but bigger molecule structure, on 336
selected MPs decreases. Therefore, the adsorbed amount of 2,4,6-TCP and PCP on PE iso- 337
lated from personal care products ranged between 47.7-66.9 µ g/g and 55.9-58.8 µ g/g, re- 338
spectively. At pH 10, the highest adsorbed amount was attained for 4-CP on powdered 339
types of MPs, about 137 µ g/g for PEp, 89.4 µ g/g for PE_PCPs_1 and 87.5 µg/g for 340
PE_PCPs_2. The adsorption affinity towered powered types of MPs decreases with an in- 341
crease of hydrophobicity and molecule structure of selected CPs at pH 10. 342
Appl. Sci. 2023, 13, x FOR PEER REVIEW 8 of 14

PEp PEN PEE

PEg PET PP PLA

a) 300 300 300

pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)
150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)

b) 300 300 300

pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)
150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)

c)
300 300 300
pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)

150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)
d)
300 300 300
pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)

150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)
343
Figure 2. Experimental data adsorption of (a) 4- CP; (b) 2,4-DCP; (c) 2,4,6-TCP and. 344
(d) PCP on PEp, PE_PCPs_1, PE_PCPs_2, PEg, PEg, PET, PP and PLA in water 345
at different pH value (n = 2, mean value _ SD) 346
347
The results shown in Figure 2 imply that selected CPs has significantly lower affinity 348
towered granulated types of MPs (6.04-202.4 µ g/g). Furthermore, pH effects are evident 349
in the adsorption behavior of all CPs on MPs. In terms of pH change, the highest impact 350
on adsorption behavior of CPs has been detected for PP, which adsorbed the lowest 351
amounts of all the CPs at pH 4 (6.04-23.3 µ g/g). The same trend for attained results, but 352
with much lower differences between the adsorbed amounts of CPs are detected for all 353
selected MPs at both pH 4 and pH 10. The lowest matrix effect was observed for PLA at 354
both pH 4 and pH 10 (17.3-45.5 µ g/g). 355
In order to get deeper informations about influence of pH change on adsorption ki- 356
netic of CPs on MPs, three kinetic models were used: pseudo-first order, pseudo-second 357
Appl. Sci. 2023, 13, x FOR PEER REVIEW 9 of 14

order and Elovich model. The results of obtained modeling data are summarized in Table 358
A4. Based on the attained results and the highest correlation coefficient (R2 = 0.862 - 0.998), 359
pseudo-second order kinetic model fitted data better than pseudo-first order and Elovich 360
models. The R2 values calculated for pseudo-second order for adsorption kinetic of 4-CP, 361
2,4-DCP, 2,4,6-TCP on seven three materials were greater than 0.900. Slightly lower R2 362
values were obtained for PCP, but the values are still high, ranging from 0.862 to 0.983. 363

PEp PEN PEE

PEg PET PP PLA

a) 300 300 300

pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)
150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)

b) 300 300 300

pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)
150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)

c)
300 300 300
pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)

150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)
d)
300 300 300
pH4 pH7 pH10
270 270 270

240 240 240

210 210 210

180 180 180

qt (µg/g)

qt (µg/g)

qt (µg/g)

150 150 150

120 120 120

90 90 90

60 60 60

30 30 30

0 0 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
t (h) t (h) t (h)
364
Figure 3. Plots for the sorption kinetics, based on the pseudo-second order model of 365
(a) 4- CP; (b) 2,4-DCP; (c) 2,4,6-TCP and (d) PCP on PEp, PE_PCPs_1, PE_PCPs_2, 366
PEg, PEg, PET, PP and PLA in water at different pH value 367
(n = 2, mean value _ SD) 368
369
Notwithstanding all the correlation coefficients values for both pseudo-first and Elo- 370
vich model within CPs experiment were higher than 0.800, pseudo-second kinetic model 371
fitted data better. Figure 2 illustrates the results of fitting the experimental data in the 372
exponential form, using pseudo-second order model, as the most appropriate. The calcu- 373
lated qe, k2, and R2 values for the pseudo-second order model are listed in Table A4. Based 374
on the results of qe values obtained with pseudo-second order model and the experimen- 375
tally attained qe values it can be concluded that this kinetic model gave the best fit for 376
attained data. Therefore, the pseudo-second order model can successfully be used to de- 377
scribe the adsorption process of the selected CPs onto MPs regardless pH value of water 378
Appl. Sci. 2023, 13, x FOR PEER REVIEW 10 of 14

from the beginning of the sorption process to the equilibrium stage. This means that CPs 379
can be adsorbed to different binding sites on the investigated MPs [20]. 380

3.4. The pH effect on adsorption isotherms of chlorinated phenols on MPs 381

The Freundlich, Langmuir models are employed to describe experimental data in ad- 382
sorption mechanism studies. The attained parameter values of isotherm models are pre- 383
sented in Table A5, while Figure 4 shows the fitting results of both Freundlich and Lang- 384
muir isotherms in the adsorption experiment of CPs on PEp, PE_PCPs_1, PE_PCPs_2PEg, 385
PEg, PET, PP and PLA in water with pH differing. 386
387
PEp PE_PCPs_1 PE_PCPs_2
PEg PET PP PLA

Freundlich model Langmuir model

a)
150 150 150
pH4 pH7 140 pH10
135 135
130
120 120 120
110
105 105
100
90 90 90
qe (µg/g)

qe (µg/g)

qe (µg/g)
80
75 75
70
60 60 60
50
45 45
40
30 30 30
20
15 15
10
0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
ce (µg/l) ce (µg/l) ce (µg/l)
b)
150 150 150
pH4 pH7 pH10
135 135 135

120 120 120

105 105 105

90 90 90
qe (µg/g)

qe (µg/g)

75 75 qe (µg/g) 75

60 60 60

45 45 45

30 30 30

15 15 15

0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
ce (µg/l) ce (µg/l) ce (µg/l)
c)
150 150 150
pH4 pH7 pH10
135 135 135

120 120 120

105 105 105

90 90 90
qe (µg/g)

qe (µg/g)

qe (µg/g)

75 75 75

60 60 60

45 45 45

30 30 30

15 15 15

0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
ce (µg/l) ce (µg/l) ce (µg/l)
d)
150 150 150
pH4 pH7 pH10
135 135 135

120 120 120

105 105 105

90 90 90
qe (µg/g)

qe (µg/g)

qe (µg/g)

75 75 75

60 60 60

45 45 45

30 30 30

15 15 15

0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
ce (µg/l) ce (µg/l) ce (µg/l)
388
Figure 4. Adsorption isotherms plots for 4-CP, b) 2,4-DCP, c) 2,4,6-TCP and d) PCP ad- 389
sorption on PEg, PEp, PET, PP and PLA in the synthetic 390
water matrix at different pH value n = 2, mean value _ SD) 391
Presented results (Table A5 and Figure 4) indicate that sorption of CPs can be de- 392
scribed well with both adsorption isotherm models, based on high R2 values obtained. The 393
values of parameter n (< 1) obtained by Freundlich model, implies a chemical adsorption 394
Appl. Sci. 2023, 13, x FOR PEER REVIEW 11 of 14

process between investigated CPs and MPs [13,20,29,35,50]. However, better correlation 395
with the Langmuir model, indicate a monolayer coverage of the sorbate over a homoge- 396
nous sorbent surface [51]. Obtained qmax values calculated using Langmuir adsorption iso- 397
therms implied that at pH 7 the highest adsorption capacity has 4-CP towered selected 398
MPs and it ranged between qmax= 33.4-205.7 µ g/g. On the other hand, for the rest of CPs, 399
2,4-DCP, 2,4,6-TCP and PCP, the highest adsorption capacity was obtained at pH 4 and it 400
ranged qmax= 15.5-198.8 µ g/g qmax= 30.4-259.9 µ g/g qmax= 25-190.6 µ g/g, respectively. Re- 401
sults for calculated qmax values are in correlation with obtained kinetic results (Figure 3 402
and table A4). Additionally, calculated KL values for Langmuir adsorption isotherms are 403
between 0 and 1 for all results impling that adsorption process of selected CPs on MPs is 404
favorable no meter the change of synthetic water matrix pH change [52], and with values 405
near zero (0.003-0.300 µ g/g) it can be postulated that process is almost irreversible. 406

4. Conclusion 407
Plastic debris has become an integral part of the environment and could serve as a 408
source of organic pollutants. Not only is it influencing the transportation of pollutants 409
through different environments, but it could also affect the way they express their toxicity 410
towards aquatic organisms and humans. The widespread application of bioplastics in eve- 411
ryday life is causing an increase in their environmental impact. It is highly important to 412
understand the interactions between various plastics and organic pollutants. 413
The findings in this study show that the presence of microplastics and bioplastics in 414
aquatic environments can have a significant impact on fate and transport of certain CPs, 415
PAHs, and halogenated benzenes. The water matrix's pH value has affected most adsorp- 416
tion behavior of CPs on all selected types of MPs, and the highest degree of adsorption 417
occurs at pH 7. Furthermore, the adsorption of halogenated benzenes and PAHs does not 418
depend on the change in the pH value of the water matrix. Besides the pH value of the 419
water matrix, sorbate's hydrophobicity has been observed to have a significant impact on 420
the adsorption affinity of halogenated benzenes and PAHs on MPs, which is one of the 421
factors that has to be taken into account. 422
423
Author Contributions: conceptualization, A.T., J.A., M.V.; methodology, A.T., M.V.; in- 424
vestigation, M.V., S.V.; Software, M.V., J.N., B.K., resources, A.T., J.A.; writing—original 425
draft preparation, M.V., A.T.; writing—review and editing, J.N., M.V.; Visualization, A.T. 426
and M.V.; project administration, A.T.; funding acquisition, A.T., J.A. 427
428
Funding: This research was funded by the Provincial 429
Secretariat for Higher Education and Scientific Research (Project No. 142- 430
451-3182/2022-01/2) and the Ministry of Education, Science and Technological Develop- 431
ment of the Republic of Serbia (Project No. III43005). 432
433
Acknowledgments: The authors acknowledge the financial support of the Provincial 434
Secretariat for Higher Education and Scientific Research (Project No. 142- 435
451-3182/2022-01/2), and the Ministry of Education, Science and Technological Develop- 436
ment of the Republic of Serbia (Project No. III43005). 437
Conflicts of Interest: The authors declare no conflict of interest. 438
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