Acrylic polymers (AP) are a diverse group of materials with broad applications, frequent use, and increasing demand. Some of the most used AP are polyacrylamide, polyacrylic acid, polymethyl ...methacrylates, and polyacrylonitrile. Although no information for the production of all AP types is published, data for the most used AP is around 9 MT/year, which gives an idea of the amount of waste that can be generated after products’ lifecycles. After its lifecycle ends, the fate of an AP product will depend on its chemical structure, the environmental setting where it was used, and the regulations for plastic waste management existing in the different countries. Even though recycling is the best fate for plastic polymer wastes, few AP can be recycled, and most of them end up in landfills. Because of the pollution crisis the planet is immersed, setting regulations and developing technological strategies for plastic waste management are urgent. In this regard, biotechnological approaches, where microbial activity is involved, could be attractive eco-friendly strategies. This mini-review describes the broad AP diversity, their properties and uses, and the factors affecting their biodegradability, underlining the importance of standardizing biodegradation quantification techniques. We also describe the enzymes and metabolic pathways that microorganisms display to attack AP chemical structure and predict some biochemical reactions that could account for quaternary carbon-containing AP biodegradation. Finally, we analyze strategies to increase AP biodegradability and stress the need for more studies on AP biodegradation and developing stricter legislation for AP use and waste control.
Key points
•
Acrylic polymers (AP) are a diverse and extensively used group of compounds.
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The environmental fates and health effects of AP waste are not completely known.
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Microorganisms and enzymes involved in AP degradation have been identified.
•
More biodegradation studies are needed to develop AP biotechnological treatments.
Glutathione (γ-glu-cys-gly; GSH) is usually present at high concentrations in most living cells, being the major reservoir of non-protein reduced sulfur. Because of its unique redox and nucleophilic ...properties, GSH serves in bio-reductive reactions as an important line of defense against reactive oxygen species, xenobiotics and heavy metals. GSH is synthesized from its constituent amino acids by two ATP-dependent reactions catalyzed by γ-glutamylcysteine synthetase and glutathione synthetase. In yeast, these enzymes are found in the cytosol, whereas in plants they are located in the cytosol and chloroplast. In protists, their location is not well established. In turn, the sulfur assimilation pathway, which leads to cysteine biosynthesis, involves high and low affinity sulfate transporters, and the enzymes ATP sulfurylase, APS kinase, PAPS reductase or APS reductase, sulfite reductase, serine acetyl transferase,
O-acetylserine/
O-acetylhomoserine sulfhydrylase and, in some organisms, also cystathionine β-synthase and cystathionine γ-lyase. The biochemical and genetic regulation of these pathways is affected by oxidative stress, sulfur deficiency and heavy metal exposure. Cells cope with heavy metal stress using different mechanisms, such as complexation and compartmentation. One of these mechanisms in some yeast, plants and protists is the enhanced synthesis of the heavy metal-chelating molecules GSH and phytochelatins, which are formed from GSH by phytochelatin synthase (PCS) in a heavy metal-dependent reaction; Cd
2+ is the most potent activator of PCS. In this work, we review the biochemical and genetic mechanisms involved in the regulation of sulfate assimilation-reduction and GSH metabolism when yeast, plants and protists are challenged by Cd
2+.
The microbial composition of polyurethane degrading communities has been barely addressed, and it is unknown if microenvironmental conditions modify its composition, affecting its biodegradative ...capacity. The polyurethanolytic activity and taxonomic composition of five microbial communities, selected by enrichment in the polyether-polyurethane-acrylic (PE-PU-A) coating PolyLack®, from deteriorated PU foams collected at different microenvironments in a municipal landfill (El Bordo Poniente, BP) were explored. All BP communities grew similarly in PolyLack® as the sole carbon source, although BP1, BP4, and BP5 showed better performance than BP2 and BP7. FTIR spectroscopy showed that ester, urethane, ether, aromatic and aliphatic groups, and the acrylate component were targets of the biodegradative activity. Extracellular esterase activity was higher at 5 days of cultivation and decreased at 21 days, while urease activity showed the opposite. Microbial composition analysis, assessed by 16S rDNA V3 region PCR-DGGE, revealed a preponderance of
Rhizobiales
and
Micrococcales
. The reported PU-degrading genera
Paracoccus
,
Acinetobacter
, and
Pseudomonas
were identified. In contrast,
Advenella
,
Bordetella
,
Microbacterium
,
Castellaniella
, and
Populibacterium
, some of them xenobiotics degraders, can be considered potentially PU-degrading genera. Correspondence analysis identified independent groups for all communities, except the BP4 and BP5. Although partial taxonomic redundancy was detected, unique OTUs were identified, e.g., three members of the
Weeksellaceae
family were present only in the BP4/BP5 group. These results suggest that the microenvironmental conditions where the landfill microbial communities were collected shaped their taxonomical composition, impacting their PE-PU biodegradative capacities. These BP communities represent valuable biological material for the treatment of PU waste and other xenobiotics.
Key points
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Landfill microbial communities display slightly different capacities for growing in polyether-polyurethane-acrylic.
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Ester, urethane, ether, aromatic, aliphatic, and acrylate groups were attacked.
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Esterase activity was more significant at early culture times while urease activity at latter.
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Landfill microenvironments shape partial taxonomical redundancy in the communities.
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Best communities’ performance seems to be related to unique members’ composition.
Polyurethanes (PU) are the sixth most produced plastics with around 18-million tons in 2016, but since they are not recyclable, they are burned or landfilled, generating damage to human health and ...ecosystems. To elucidate the mechanisms that landfill microbial communities perform to attack recalcitrant PU plastics, we studied the degradative activity of a mixed microbial culture, selected from a municipal landfill by its capability to grow in a water PU dispersion (WPUD) as the only carbon source, as a model for the BP8 landfill microbial community. The WPUD contains a polyether-polyurethane-acrylate (PE-PU-A) copolymer and xenobiotic additives (
-methylpyrrolidone, isopropanol and glycol ethers). To identify the changes that the BP8 microbial community culture generates to the WPUD additives and copolymer, we performed chemical and physical analyses of the biodegradation process during 25 days of cultivation. These analyses included Nuclear magnetic resonance, Fourier transform infrared spectroscopy, Thermogravimetry, Differential scanning calorimetry, Gel permeation chromatography, and Gas chromatography coupled to mass spectrometry techniques. Moreover, for revealing the BP8 community structure and its genetically encoded potential biodegradative capability we also performed a proximity ligation-based metagenomic analysis. The additives present in the WPUD were consumed early whereas the copolymer was cleaved throughout the 25-days of incubation. The analysis of the biodegradation process and the identified biodegradation products showed that BP8 cleaves esters, C-C, and the recalcitrant aromatic urethanes and ether groups by hydrolytic and oxidative mechanisms, both in the soft and the hard segments of the copolymer. The proximity ligation-based metagenomic analysis allowed the reconstruction of five genomes, three of them from novel species. In the metagenome, genes encoding known enzymes, and putative enzymes and metabolic pathways accounting for the biodegradative activity of the BP8 community over the additives and PE-PU-A copolymer were identified. This is the first study revealing the genetically encoded potential biodegradative capability of a microbial community selected from a landfill, that thrives within a WPUD system and shows potential for bioremediation of polyurethane- and xenobiotic additives-contamitated sites.
Increased oxidative stress displayed during dark-senescence of wheat leaves (
Triticum aestivum L.) is caused not only by the increased levels of radicals but also by a loss of antioxidant capacity. ...Mature leaves were incubated in 6-benzylaminopurine (BAP 10
−4
M) or water (control) during 6
d in the dark. The senescence-delaying effect of BAP was associated with the retention of the chloroplast structure, 60% of the initial content of chlorophyll (Chl) and 77% of the initial content of protein. BAP reduced the degradation of the light-harvesting chlorophyll
a/
b binding protein (LHCP-2), and the large (LSU) and small subunits (SSU) of Rubisco. Our results indicated that the presence of the NADPH:protochlorophyllide oxidoreductase (POR, EC.1.6.99.1) was not promoted by the cytokinin, leading to the conclusion that BAP maintains the level of Chl, preventing its degradation, rather than inducing Chl biosynthesis. The internal structure of chloroplasts was maintained in BAP-treated leaves for up to 6
d, with well-organized grana thylakoids and small plastoglobuli; in contrast, chloroplasts of control leaves deteriorated rapidly from day 4 with disorganized internal membranes, and more and larger plastoglobuli. BAP increased the activities of catalase (CAT, EC 1.11.1.6) and ascorbate peroxidase (APX, EC 1.11.1.11) and reduced the level of H
2O
2 in the delayed-senescence tissue. The present research indicates that BAP reduces levels of reactive oxygen species (ROS), and enhances the activity of antioxidant enzymes (CAT, APX). Our results suggest that BAP protects the cell membranes and the photosynthetic machinery from oxidative damage during delay of senescence in the dark.
Microbial communities are more effective in degrading natural polymers and xenobiotics than pure cultures. Biodegradation of polyacrylic and polyurethane polymers by bacterial and fungal strains has ...been addressed, but limited information about their biodegradation by microbial communities exists. The aim of this work was to evaluate the ability of three enriched microbial communities (BP1h, BP3h, and BP7h), selected from deteriorated foam pieces collected in a landfill, to biodegrade the polyacrylic component of the 2K-PU coating Bayhydrol® A2470 and the polyester polyurethane coating NeoRez™ R-9637. Two communities were further selected to quantify extracellular esterase, protease, and urease activities, to identify their taxonomic composition, and to analyze the ability of their isolated members to grow in those polymers. The growth of the three communities was larger in polyester polyurethane than in polyacrylic and their biodegradative activities affected ester, urethane, ether, aromatic, and aliphatic groups of the compounds present in the coatings. From all the communities growing in polyacrylic or in polyester polyurethane, two and five different types of colonies were isolated, respectively. In polyacrylic, extracellular esterase and protease activities were at their maximum level at 7 days of culture, whereas in polyester polyurethane, protease and urease were greatest at 21 days. All the isolated community members were identified as xenobiotics degraders. The complete communities grew better in media with the polymers than the isolated members. This is one of the few studies reporting biodegradation of synthetic polymers by microbial communities and serves as basis for developing synthetic consortia with enhanced degradative abilities.
Due to its wide industrial use, chromium is considered a serious environmental pollutant. Contamination of soil and water by chromium (Cr) is of recent concern. Toxicity of Cr to plants depends on ...its valence state: Cr(VI) is highly toxic and mobile whereas Cr(III) is less toxic. Since plants lack a specific transport system for Cr, it is taken up by carriers of essential ions such as sulfate or iron. Toxic effects of Cr on plant growth and development include alterations in the germination process as well as in the growth of roots, stems and leaves, which may affect total dry matter production and yield. Cr also causes deleterious effects on plant physiological processes such as photosynthesis, water relations and mineral nutrition. Metabolic alterations by Cr exposure have also been described in plants either by a direct effect on enzymes or other metabolites or by its ability to generate reactive oxygen species which may cause oxidative stress. The potential of plants with the capacity to accumulate or to stabilize Cr compounds for bioremediation of Cr contamination has gained interest in recent years.
Two bacterial strains (BQ1 and BQ8) were isolated from decomposed soft foam. These were selected for their capacity to grow in a minimal medium (MM) supplemented with a commercial surface-coating ...polyurethane (PU) (Hydroform) as the carbon source (MM-PUh). Both bacterial strains were identified as Alicycliphilus sp. by comparative 16S rRNA gene sequence analysis. Growth in MM-PUh showed hyperbolic behavior, with BQ1 producing higher maximum growth (17.8 ± 0.6 mg·ml⁻¹) than BQ8 (14.0 ± 0.6 mg·ml⁻¹) after 100 h of culture. Nuclear magnetic resonance, Fourier transform infrared (IR) spectroscopy, and gas chromatography-mass spectrometry analyses of Hydroform showed that it was a polyester PU type which also contained N-methylpyrrolidone (NMP) as an additive. Alicycliphilus sp. utilizes NMP during the first stage of growth and was able to use it as the sole carbon and nitrogen source, with calculated Ks values of about 8 mg·ml⁻¹. Enzymatic activities related to PU degradation (esterase, protease, and urease activities) were tested by using differential media and activity assays in cell-free supernatants of bacterial cultures in MM-PUh. Induction of esterase activity in inoculated MM-PUh, but not that of protease or urease activities, was observed at 12 h of culture. Esterase activity reached its maximum at 18 h and was maintained at 50% of its maximal activity until the end of the analysis (120 h). The capacity of Alicycliphilus sp. to degrade PU was demonstrated by changes in the PU IR spectrum and by the numerous holes produced in solid PU observed by scanning electron microscopy after bacterial culture. Changes in the PU IR spectra indicate that an esterase activity is involved in PU degradation.
Polyurethane (PU) is widely used in many aspects of modern life because of its versatility and resistance. However, PU waste disposal generates large problems, since it is slowly degraded, there are ...limited recycling processes, and its destruction may generate toxic compounds. In this work, we isolated fungal strains able to grow in mineral medium with a polyester PU (PS-PU; Impranil DLN) or a polyether PU (PE-PU; Poly Lack) varnish as the only carbon source. Of the eight best Impranil-degrading strains, the six best degraders belonged to the Cladosporium cladosporioides complex, including the species C. pseudocladosporioides, C. tenuissimum, C. asperulatum, and C. montecillanum, and the two others were identified as Aspergillus fumigatus and Penicillium chrysogenum The best Impranil degrader, C. pseudocladosporioides strain T1.PL.1, degraded up to 87% after 14 days of incubation. Fourier transform infrared (FTIR) spectroscopy analysis of Impranil degradation by this strain showed a loss of carbonyl groups (1,729 cm(-1)) and N-H bonds (1,540 and 1,261 cm(-1)), and gas chromatography-mass spectrometry (GC-MS) analysis showed a decrease in ester compounds and increase in alcohols and hexane diisocyanate, indicating the hydrolysis of ester and urethane bonds. Extracellular esterase and low urease, but not protease activities were detected at 7 and 14 days of culture in Impranil. The best eight Impranil-degrading fungi were also able to degrade solid foams of the highly recalcitrant PE-PU type to different extents, with the highest levels generating up to 65% of dry-weight losses not previously reported. Scanning electron microscopy (SEM) analysis of fungus-treated foams showed melted and thinner cell wall structures than the non-fungus-treated ones, demonstrating fungal biodegradative action on PE-PU.
Polyurethane waste disposal has become a serious problem. In this work, fungal strains able to efficiently degrade different types of polyurethanes are reported, and their biodegradative activity was studied by different experimental approaches. Varnish biodegradation analyses showed that fungi were able to break down the polymer in some of their precursors, offering the possibility that they may be recovered and used for new polyurethane synthesis. Also, the levels of degradation of solid polyether polyurethane foams reported in this work have never been observed previously. Isolation of efficient polyurethane-degrading microorganisms and delving into the mechanisms they used to degrade the polymer provide the basis for the development of biotechnological processes for polyurethane biodegradation and recycling.
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