Injection-Molded Bioblends from Lignin and Biodegradable Polymers: Processing and Performance Evaluation

This paper investigates the effects of the incorporation of lignin and small quantities of epoxidized natural rubber (ENR) as an impact modifying agent on blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL). The addition of lignin resulted in a slight improvement of flexural strength and modulus of the ternary blending system. Incorporation of ENR into the blend resulted in an increase in notched Izod impact strength from 40 to 135% depending on the concentration of ENR. The addition of lignin into the blend resulted in an improvement of thermal stability of the ternary blend system. Morphological analysis showed a good dispersion of PHBV phases and lignin within the PCL matrix. Rheological characterization revealed that the presence of lignin resulted in increased storage modulus of the bioblend.     

Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of \({\text{UO}}_{2}^{{2+}}\) from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of \({\text{UO}}_{2}^{{2+}}\) by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R²?=?0.99) and probability F-values (F?=?2.24?×?10^??10) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of \({\text{UO}}_{2}^{{2+}}\) ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.     

Thermally Stable Pyrolytic Biocarbon as an Effective and Sustainable Reinforcing Filler for Polyamide Bio-composites Fabrication

Natural fibers are limited in their use as reinforcement to commodity polymers. They cannot be used to reinforce engineering polymers due to their low thermal stability at high processing temperatures. This study presents an approach to successfully reinforce polyamides using a derivative of natural fibers as reinforcement without the effects of thermal degradation during melt processing. Biocarbon from miscanthus fibers was used to reinforce polyamide 6 up to 40 wt%. At 40 wt% filler content, the tensile and flexural strengths increased by 19.6 and 47% respectively in comparison to the neat polyamide. The moduli were also increased by 31.5 and 63.7% respectively. A maximum increase in impact strength of 43.7% was achieved at 20 wt% biocarbon loading. The morphology of the tensile fractured samples showed stretched polyamide ligaments attached to the biocarbon particles, indicating the presence of interaction between filler and matrix. Interestingly, more bonded interfaces were observed between the polyamide and biocarbon particles with increasing biocarbon content possibly stemming from increased biocarbon surfaces with functional groups. These composites show great potential to substitute in part or whole, some particulate filled polyamides currently used in the automotive industry.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

Preparation and Characterization of Xylan Derivatives and Their Blends

Although hemicellulose is found widely in nature, it is currently under-utilized as a raw material for commercial applications. It would be desirable to find new uses for hemicellulose in order to add value to this agro-based material. A common type of hemicellulose is xylan, which is found in a number of wood species and in cotton. In this work we prepared cationic and anionic xylan derivatives and characterized them by ¹³C NMR, FT-IR, size exclusion chromatography (SEC), thermal analysis, and rheology. In particular, the ¹³C NMR spectra of carboxymethyl xylan (CMX) and quaternary ammonium-adducted xylan (QAX) were fully assigned with the help of samples with different degrees of substitution. SEC indicated that the beechwood xylan showed a bimodal molecular weight distribution, but with derivatization the distribution tended to become unimodal. Thermal analysis and rheology studies did not uncover any surprises; the solution of xylan and its derivatives exhibited mostly Newtonian behavior. The blends of CMX and QAX produced a precipitate at almost all ratios, indicating the formation of a polyelectrolyte complex. When cationic and anionic xylan samples were added together to paper, the paper dry strength increased. Thus, the combination of cationic/anionic xylan may be of interest in selected applications.     

Long-term dispersion and availability of metals from submarine mine tailing disposal in a fjord in Arctic Norway

Mining of Cu took place in Kvalsund in the Arctic part of Norway in the 1970s, and mine tailings were discharged to the inner part of the fjord, Repparfjorden. Metal speciation analysis was used to assess the historical dispersion of metals as well as their potential bioavailability from the area of the mine tailing disposal. It was revealed that the dispersion of Ba, Cr, Ni, Pb and Zn from the mine tailings has been limited. Dispersion of Cu to the outer fjord has, however, occurred; the amounts released and dispersed from the mine tailing disposal area quantified to be 2.5–10 t, less than 5% of Cu in the original mine tailings. An estimated 80–390 t of Cu still remains in the disposal area from the surface to a depth of 16 cm. Metal partitioning showed that 56–95% of the Cu is bound in the potential bioavailable fractions (exchangeable, reducible and oxidisable) of the sediments, totalling approximately 70–340 t, with potential for continuous release to the pore water and re-precipitation in over- and underlying sediments. Surface sediments in the deposit area were affected by elevated Cu concentrations just above the probable effect level according to the Norwegian sediment quality criteria, with 50–80% Cu bound in the exchangeable, reducible and oxidisable fractions, potentially available for release to the water column and/or for uptake in benthic organisms.     

Water quality and health in northern Canada: stored drinking water and acute gastrointestinal illness in Labrador Inuit

One of the highest self-reported incidence rates of acute gastrointestinal illness (AGI) in the global peer-reviewed literature occurs in Inuit communities in the Canadian Arctic. This high incidence of illness could be due, in part, to the consumption of contaminated water, as many northern communities face challenges related to the quality of municipal drinking water. Furthermore, many Inuit store drinking water in containers in the home, which could increase the risk of contamination between source and point-of-use (i.e., water recontamination during storage). To examine this risk, this research characterized drinking water collection and storage practices, identified potential risk factors for water contamination between source and point-of-use, and examined possible associations between drinking water contamination and self-reported AGI in the Inuit community of Rigolet, Canada. The study included a cross-sectional census survey that captured data on types of drinking water used, household practices related to drinking water (e.g., how it was collected and stored), physical characteristics of water storage containers, and self-reported AGI. Additionally, water samples were collected from all identified drinking water containers in homes and analyzed for presence of Escherichia coli and total coliforms. Despite municipally treated tap water being available in all homes, 77.6% of households had alternative sources of drinking water stored in containers, and of these containers, 25.2% tested positive for total coliforms. The use of transfer devices and water dippers (i.e., smaller bowls or measuring cups) for the collection and retrieval of water from containers were both significantly associated with increased odds of total coliform presence in stored water (OR_{transfer device} = 3.4, 95% CI 1.2–11.7; OR_dipper = 13.4, 95% CI 3.8–47.1). Twenty-eight-day period prevalence of self-reported AGI during the month before the survey was 17.2% (95% CI 13.0–22.5), which yielded an annual incidence rate of 2.4 cases per person per year (95% CI 1.8–3.1); no water-related risk factors were significantly associated with AGI. Considering the high prevalence of, and risk factors associated with, indicator bacteria in drinking water stored in containers, potential exposure to waterborne pathogens may be minimized through interventions at the household level.     

Enhanced photocatalytic activity using GO/TiO<Subscript>2</Subscript> catalyst for the removal of DCA solutions

This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO₂) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO₂ photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO₂ ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO₂ was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO₂. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO₂ weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO₂, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.