Concept: Linear low-density polyethylene
Concerns regarding marine plastic pollution and its affinity for chemical pollutants led us to quantify relationships between different types of mass-produced plastic and organic contaminants in an urban bay. At five locations in San Diego Bay, CA we measured sorption of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) throughout a 12-month period to the five most common types of mass-produced plastic: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP). During this long-term field experiment, sorption rates and concentrations of PCBs and PAHs varied significantly among plastic types and among locations. Our data suggest that for PAHs and PCBs, PET and PVC reach equilibrium in the marine environment much faster than HDPE, LDPE and PP. Most importantly, concentrations of PAHs and PCBs sorbed to HDPE, LDPE and PP were consistently much greater than concentrations sorbed to PET and PVC. These data imply that products made from HDPE, LDPE and PP pose a greater risk than products made from PET and PVC of concentrating these hazardous chemicals onto fragmented plastic debris ingested by marine animals.
The influence of PBR composition [clear polyurethane (PolyU) vs. clear linear low-density polyethylene (LLDPE) (top) and black opaque high-density polyethylene (bottom)] and shape (rectangular vs. tubular) on biofouling and the influence of biofouling on algae productivity were investigated. In 9-week experiments, PBR biofouling was dominated by pennate diatoms and clear plastics developed macroalgae. LLDPE exhibited lower photosynthetic-active-radiation (PAR) light transmittance than PolyU before biofouling, but higher transmittance afterwards. Both rectangular and tubular LLDPE PBRs accumulated biofouling predominantly along their wetted edges. For a tubular LLDPE PBR after 12weeks of biofouling, the correlation between biomass, percent surface coverage, and PAR transmittance was complex, but in general biomass inversely correlated with transmittance. Wrapping segments of this biofouled LLDPE around an algae culture reduced CO2 and NH3-N utilization, indicating that external biofouling must be controlled.
This study investigated the potential of bacterial-mediated polyethylene (PE) degradation in a two-phase microcosm experiment. During phase I, naturally weathered PE films were incubated for 6 months with the indigenous marine community alone as well as bioaugmented with strains able to grow in minimal medium with linear low-density polyethylene (LLDPE) as the sole carbon source. At the end of phase I the developed biofilm was harvested and re-inoculated with naturally weathered PE films. Bacteria from both treatments were able to establish an active population on the PE surfaces as the biofilm community developed in a time dependent way. Moreover, a convergence in the composition of these communities was observed towards an efficient PE degrading microbial network, comprising of indigenous species. In acclimated communities, genera affiliated with synthetic (PE) and natural (cellulose) polymer degraders as well as hydrocarbon degrading bacteria were enriched. The acclimated consortia (indigenous and bioaugmented) reduced more efficiently the weight of PE films in comparison to non-acclimated bacteria. The SEM images revealed a dense and compact biofilm layer and signs of bio-erosion on the surface of the films. Rheological results suggest that the polymers after microbial treatment had wider molecular mass distribution and a marginally smaller average molar mass suggesting biodegradation as opposed to abiotic degradation. Modifications on the surface chemistry were observed throughout phase II while the FTIR profiles of microbially treated films at month 6 were similar to the profiles of virgin PE. Taking into account the results, we can suggest that the tailored indigenous marine community represents an efficient consortium for degrading weathered PE plastics.
Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of (m) CPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C-C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C-H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and (m) CPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting properties and serve as macroinitiators to synthesize graft polycaprolactones that compatibilize polyethylene-polycaprolactone blends.
Polycyclic aromatic hydrocarbons (PAHs) on virgin polystyrene (PS) and PS marine debris led us to examine PS as a source and sink for PAHs in the marine environment. At two locations in San Diego Bay, we measured sorption of PAHs to PS pellets, sampling at 0, 1, 3, 6, 9, and 12 months. We detected 25 PAHs using a new analytical method with comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. Several congeners were detected on samples before deployment. After deployment, some concentrations decreased (1,3-dimethylnaphthalene and 2,6-methylnaphthalene), while most increased [2-methylanthracene and all parent PAHs (PPAHs), except fluorene and fluoranthene], suggesting that PS debris is a source and sink for PAHs. When sorbed concentrations of PPAHs on PS are compared to the five most common polymers [polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP)], PS sorbed greater concentrations than PP, PET, and PVC, similar to HDPE and LDPE. Most strikingly, at 0 months, PPAHs on PS ranged from 8 to 200 times greater than on PET, HDPE, PVC, LDPE, and PP. The combination of greater PAHs in virgin pellets and large sorption suggests that PS may pose a greater risk of exposure to PAHs upon ingestion.
Antimicrobial surfaces are one approach to prevent biofilms in the food industry. The aim of this study was to investigate the effect of poly((tert-butyl-amino)-methyl-styrene) (poly(TBAMS)) incorporated into linear low-density polyethylene (LLDPE) on the formation of mono- and mixed-species biofilms. The biofilm on untreated and treated LLDPE was determined after 48 and 168 h. The comparison of the results indicated that the ability of Listeria monocytogenes to form biofilms was completely suppressed by poly(TBAMS) (Δ168 h 3.2 log10 cfu cm-2) and colonization of Staphylococcus aureus and Escherichia coli was significantly delayed, but no effect on Pseudomonas fluorescens was observed. The results of dual-species biofilms showed complex interactions between the microorganisms, but comparable effects on the individual bacteria by poly(TBAMS) were identified. Antimicrobial treatment with poly(TBAMS) shows great potential to prevent biofilms on polymeric surfaces. However, a further development of the material is necessary to reduce the colonization of strong biofilm formers.
The influence of polymer aging, water pH, and aqueous Pb concentration on Pb deposition onto low density polyethylene (LDPE) was investigated. LDPE pellets were aged by ozonation at 85 °C. ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis of aged LDPE surfaces showed that a variety of polar functional groups (>CO<, >CO, >COO) were formed during aging. These functional groups likely provided better nucleation sites for Pb(OH)2deposition compared to new LDPE, which did not have these oxygen-containing functional groups. The type and amount of Pb species present on these surfaces were evaluated through XPS. The influence of exposure duration on Pb deposition onto LDPE was modeled using the pseudo-first-order equation. Distribution ratios of 251.5 for aged LDPE and 69.3 for new LDPE showed that Pb precipitates had greater affinity for the surface of aged LDPE compared to new LDPE. Aged LDPE had less Pb surface loading at pH 11 compared to loading at pH 7.8. Pb surface loading for aged LDPE changed linearly with aging duration (from 0.5-7.5 h). Pb surface loading on both new and aged LDPE increased linearly with increasing Pb initial concentration. Greater Pb precipitation rates were found for aged LDPE compared to new LDPE at both tested pH values.
Polyolefins that contain polar functionality are important materials for next-generation, lightweight engineering thermoplastics. Post-polymerization modification is an ideal method for the incorporation of polar groups onto branched polyolefins; however, it typically results in chain scission events that have deleterious effects on polymer properties. Herein, we report a metal-free method for radical-mediated C-H xanthylation that results in regioselective functionalization of branched polyolefins without coincident polymer chain scission. The method enables a tunable degree of polymer functionalization and capitalizes on the versatility of the xanthate functional group to unlock a wide variety of C-H transformations previously inaccessible on branched polyolefins. This approach is amenable to commercial polyolefin substrates such as high-density polyethylene and linear low-density polyethylene.
Identification and quantitation of semi-crystalline microplastics using image analysis and differential scanning calorimetry
- Environmental science and pollution research international
- Published 3 months ago
There are several techniques used to analyze microplastics. These are often based on a combination of visual and spectroscopic techniques. Here we introduce an alternative workflow for identification and mass quantitation through a combination of optical microscopy with image analysis (IA) and differential scanning calorimetry (DSC). We studied four synthetic polymers with environmental concern: low and high density polyethylene (LDPE and HDPE, respectively), polypropylene (PP), and polyethylene terephthalate (PET). Selected experiments were conducted to investigate (i) particle characterization and counting procedures based on image analysis with open-source software, (ii) chemical identification of microplastics based on DSC signal processing, (iii) dependence of particle size on DSC signal, and (iv) quantitation of microplastics mass based on DSC signal. We describe the potential and limitations of these techniques to increase reliability for microplastic analysis. Particle size demonstrated to have particular incidence in the qualitative and quantitative performance of DSC signals. Both, identification (based on characteristic onset temperature) and mass quantitation (based on heat flow) showed to be affected by particle size. As a result, a proper sample treatment which includes sieving of suspended particles is particularly required for this analytical approach.
A hierarchical classification approach for recognition of low-density (LDPE) and high-density polyethylene (HDPE) in mixed plastic waste based on short-wave infrared (SWIR) hyperspectral imaging
- Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy
- Published 3 months ago
The aim of this work was to recognize different polymer flakes from mixed plastic waste through an innovative hierarchical classification strategy based on hyperspectral imaging, with particular reference to low density polyethylene (LDPE) and high-density polyethylene (HDPE). A plastic waste composition assessment, including also LDPE and HDPE identification, may help to define optimal recycling strategies for product quality control. Correct handling of plastic waste is essential for its further “sustainable” recovery, maximizing the sorting performance in particular for plastics with similar characteristics as LDPE and HDPE. Five different plastic waste samples were chosen for the investigation: polypropylene (PP), LDPE, HDPE, polystyrene (PS) and polyvinyl chloride (PVC). A calibration dataset was realized utilizing the corresponding virgin polymers. Hyperspectral imaging in the short-wave infrared range (1000-2500nm) was thus applied to evaluate the different plastic spectral attributes finalized to perform their recognition/classification. After exploring polymer spectral differences by principal component analysis (PCA), a hierarchical partial least squares discriminant analysis (PLS-DA) model was built allowing the five different polymers to be recognized. The proposed methodology, based on hierarchical classification, is very powerful and fast, allowing to recognize the five different polymers in a single step.