The experiments to determine the weight loss of the treated PET and PE samples under composting conditions are summarized in Fig. 2 (a) and (b), respectively. The samples were recovered every five (5) days from the compost incubated at 58.0 ± 1.0°C. The weight loss in the samples at each specific time was calculated with respect to the weight of the initial samples (D0). A statistically significant change in the weight loss for the treated PET samples at 25 days (D25) was observed. The results indicated a progressive gain of weight on the samples from D15 to D25. This fact could be related with an adhesion of the compost material on the surface of the samples, which is unlikely given by a change in the physical parameters of the compost (temperature fluctuations or increased humidity). However, this effect was not noticed in the samples at longer treatment (incubation) times (D30 to D90), where no statistically significative changes in the weight were observed.
In the case of treated PE samples, the statistical analysis did not reveal any effect on plastic degradation over treatment time. The results showed that the composting conditions with a coffee pulp as substrate had no significant effect on the degradation of the plastics over the total time evaluated in this study (90 days). The degradation processes under composting conditions are influenced by factors not only include the physicochemical characteristics of the plastics under study, as their molecular structure, molecular weight, degree of crystallinity and melting temperature of polymer but also own factors in terms of the variation of the soil, organic and inorganic compositions of the compost employed as well as the types of degrading microbiota and the incubation temperature [2].
Some previous studies on polymer degradation of PET and PE under natural and composting conditions have not evidenced a significant degradation of the plastics[1], [11], [17], [18] The effect of biodegradable materials as PLA, PHB or TPS in the recycling process of PET was studied by Aldas et al.[18] Their results showed that these biodegradable polymers had not effect on the degradation of PET under the composting conditions used in that case. On the contrary, the presence of PET interferes with the degradation process of the biodegradable polymers under composting conditions, observed by thermogravimetric analysis, since the degradation temperature of the blends decreased only a few degrees and the samples did not show a significant weight loss after 30 days of treatment. On the other hand, a study of the biodegradable kinetics of PE under controlled composting conditions evidenced that the surface of PE and PE/starch remained unchanged after the treatment [11], [19]. These observations showed that the study of weight loss alone is insufficient to determine the degradation degree of plastics. Thereby, the evaluation of the physicochemical and structural properties by using other characterization techniques as FT-IR, SEM or TGA enable to identify specific behaviour that is only evidenced in detail through those techniques, and it will elucidate changes in the plastic samples subjected to composting treatment [20]. On the other hand, to understand how degradation processes of the plastic considered non-degradable occur under composting conditions, the determination of the parameters and conditions of the compost, nature, and environment where composting happen are relevant factors to get an effective process of degradation or disintegration of the plastics without a pre-treatment.
A detailed FT-IR analysis of the treated samples allowed us to assess the effect of composting conditions as a function of time, checking the variation in the intensity and position of the bands assigned to the vibrations of the functional groups of PET and PE samples [21]. The FT-IR spectra for PET at different time of composting are shown in the Fig. 3 (a). As can be seen, there are no appreciable changes in the spectra of treated samples of PET in comparison with the initial plastic material. So, the intense band at around 1714 cm− 1 is associated to strong carbonyl bond stretching of -C = O group[22], [23] whereas the broad and intense bands at 1240 cm− 1 and 1095 cm− 1 are assigned to the typical stretching vibrations of ether C–O–C[22] and esther[23], [24] bonds, respectively. The C—C stretching aromatic bonds appeared at a wavenumber of 1409 cm− 1 [25], while the band of low intensity at 1338 cm− 1 is associated to wagging of the ethylene units[22]. At lower wavenumbers, the FT-IR spectra showed an intense band at 1017 cm− 1 that can be assigned to C-H aromatic ring in plane bending[24] The band at 970 cm− 1 have been assigned to -C-C- and -C = C- bonds[26] or to -O-CH2- stretching of ethylene glycol segments [27]. The bands at 871 and 846 cm− 1 are attributed to out of plane bending of C-H aromatic ring[28] and rocking bending of C-H bonds of –CH2- [29], respectively, whereas the band at 723 cm− 1is assigned to the aromatic in-phase -C-H- out-of- plane bend [22], [23], [30].
The FT-IR spectra of treated PE samples shown in Fig. 3 (b) did not reveal significant changes in their bands as a function of the treatment time. The spectra present the following main transmittance bands at 2914 and 2848 cm− 1 correspond to the C-H stretching vibrations bonds, the bands at 1471 and 719 cm− 1 are associated to the bending and rocking vibration, respectively, of the -CH2- bonds in the polymer [23], [31]. The fact that PE samples treated under composting conditions showed a similar behaviour to that observed in treated PET samples indicated that no significative chemical changes took place owing to the treatment.
The thermal stability and decomposition of the samples were evaluated by TG/DTA at different treatment times. The TG/DTA curves and the degradation temperatures for PET and PE samples during composting treatment over time are shown in Fig. 4 (a) and (b), respectively. The PET samples undergoes two stages of degradation, the first one with a maximum around 418°C and a weight loss of 83.0% due to the thermal degradation of the PET backbone owing to the random scission of ester links in the main chain with the formation of different oligomers, and a second one at 547°C with a weight loss of 17.0% [18], [32]–[34]. All treated PET samples under composting conditions showed a similar trend in the thermogravimetric analysis. This indicates that the thermal stability of the treated PET samples was inappreciably affected for the composting treatment. Similar results were also reported by Girija et al.[33] who investigated the thermal and mechanical properties of PET blends with various natural polymers like starch or cellulose derivatives compounds and they found that there were no significant changes in the decomposition temperature of PET in the blends.
However, in the case of treated PE samples, the thermogravimetric analysis showed different behaviours for thermal degradation of this polymer as a function of time under composting conditions in contrast with those of PET. The thermal degradation mostly occurred in four stages on PE samples as can be seen in Fig. 4(b). For the initial sample (D0), the maximum degradation rate took place at 357°C with a weight loss of 38.0%, followed by a second stage at 380°C with a weight loss of 25.0%, the third one at 449°C with a weight loss of 28.0%, and a last one around of 533°C with a weight loss of 9%. For the treated PE sample at 20 days (D20), the main decomposition took place in the second stage at 341°C and a weight loss of 37%. For this sample, the thermal degradation happened at lower temperatures than no-treated PE sample (D0). As composting time increase, for example D60 and D90 samples, the higher thermal degradation occurred in the first stage as in D0, at 358°C and 359°C and a weight loss of 57% and 69%, respectively.
These differences between the thermal behaviour of treated PET and PE samples could be due to the chemical structure of PE used for packaging (low-density polyethylene, LDPE). Its less compact structure with a lot of branches [35] gives place to a random and distinct interactions of the plastic with the surrounding environment. As a consequence of these interactions, the polyethylene decomposes and results in a random distribution of volatile matters which contain not only different hydrocarbons but also organic residues and microorganisms from the compost. This consideration agrees with the higher thermal stability against degradation observed for treated PET samples under composting conditions, since PET plastic has a higher degree of polymerization than PE plastic [36], [37]
The effect of the composting process on PET and PE samples was monitored by SEM images and by digital photos to analyse and to detect changes in the morphology as a function of the treatment time The digital photos of the surface appearance of treated PET samples are shown Fig. 5 (insets). As can be seen, the samples lost stiffness as the treatment time increase. The plastic samples began to curve at 20 days (D20), and this change in the appearance was more evident at 90 days (D90) of treatment under composting conditions. On the other hand, after 30 days of composting, the treated PET samples evidenced some brown areas on their surface. This result would be related to the adhesion of the organic matter from the compost to the surface of the samples, which increased at long treatment times (D90). The SEM images of the surfaces showed a uniform and smooth aspect until the sample D20 of composting. However, from D30 to D90 horizontal and vertical stripes were observed, as well as a change in the surface roughness of the plastic, which could probably also be a consequence of the adhesion of the compost on the surface of the samples, as it has been mentioned above. Furthermore, this effect of composting observed by microscopy agrees with the fact that D30 showed an increase in its weight, according to Fig. 2(a), which would highlight that the adhesion of the compost on the surface of the plastic could hide or reduce the response of the polymer to the degradation process. At the end of the treatment time, samples D80 and D90, a layer of compost can be observed on the surface. This observation well-coincides with tonality changes and the appearance of brown spots on the surface of the plastic.
The appearance and morphologic changes in treated PE samples are shown in Fig. 6. In this case, the effect of the composting on the surface of the samples was exhibited early than for treated PET samples. The surface of the samples became rough from 10 days of treatment (D10), and random stripes and adhesion of compost on the surface took place at an early stage in the process. Other significant changes in the appearance of the PE samples were the changes in the tonality towards brown colour on most of the samples, like what happened in treated PET samples. From the above observations in appearance and surface morphology changes it may be concluded that the treated PE and PET samples remained unchanged. They did not exhibit changes related to degradation after composting treatment such as erosion on them, which would indicate that they were not attacked by the microorganisms under the composting conditions established in this study. These results are consistent with FT-IR and weight loss analysis which evidenced that the degradation of PE and PET was negligible[11], [38]. Furthermore, the adhesion observed by microscopy (SEM) was in good agreement with thermogravimetric analysis over testing time. It is necessary to point out that the variation of the weight loss on these samples would be related with the amount of compost attached on the surface under composting conditions. The negligible weight loss of PE samples as a function of composting time, displayed in the Fig. 2(b), the physical characteristics of this plastic and the difference on the surface area in contact with the compost, would cause this effect (compost adhesion) to appear in an early stage of the treatment in comparison with those of PET.
Microbiological Analysis Of Compost
The 16S rRNA gene clone analysis was used to identify the bacterial community in compost containing coffee pulp as substrate, that was used for the composting processes of PET and PE samples after 90 days. The classification analysis and relative abundance of bacteria at the phylum, family, and genus levels (taxonomic groups in the classification of organisms) are shown in Fig. 7. As can be seen, Proteobacteria, Bacteriodota, Actinobacteriota, Firmicutes, Chloroflexi and Myxococcota were the six most dominant phylum in the compost samples. Between them, Proteobacteria and Bacteroidota were the most abundant phylum with around 55.0%, whereas Myxococcota only contribute with a 1.0% of the bacterial content in the compost.
In terms of family, the analysis of the relative abundance revealed that Sphingobacteriaceae was the most abundant family, with a 21.0% of the total bacterial 16S r RNA sequence, followed by Rhizobiaceae, Streptosporangiaceae and Flavobacteriaceae which contributed to 9.0% each to the bacterial population in the compost.
Lastly, Planococcaceae and Bacillacea have the lower proportion on the composition of bacterial communities. Sphingobacterium (∼20.0%) and Nonomuraea (10.0%) comprised the main genera bacterial composition in the compost.
In a previous paper has been reported that the Proteobacteria, Firmicutes and Actinobacteria are the most abundant phyla bacterial communities found during composting processes[39] as in the findings of this research. However, it has been reported that species belonging to the genera, like Pseudomons, Ralstonia, Stenotrophomonas, Klebsiella, Acinetobact, Rodococcus, Staphylococcus, Streptococcus, Stretomyces and Bacillus, are able to degrade some types of PE [1], [4], [10], [14], [40]. However, they were not found in the compost medium employed in this study for PET and PE samples. Some of these bacterial communities were also found in the microbial structure sequencing during spontaneous coffee-bean fermentation process in Colombia [41]. Therefore, the lack of this kind of the bacterial communities in the compost after composting processes of PET and PE samples could be related with their negligible degradation and disintegration, considering that composting physical conditions like humidity and temperature play a crucial role not just for degradation of polymer materials, influenced by the nature of each plastic, but also for effective action of the microorganisms present in the compost [1], [11], [38], [40], [42]. On the other hand, it has been reported that the growth of microbial community controlled under certain laboratory conditions (constant abiotic conditions) of temperature, humidity, and aeration, can have a grave impact on the activity of the microorganism for the degradation processes of plastics [40]. Thereby, to determine the nature of the environment where the process occurs will allow to control and fit the best conditions to reach it and guarantees more reproducible results.