Applicability of Titanium-Based Catalysts in the Photocatalytic Degradation of 2,3,7,8-Tetrachlorodibenzofuran.

Polychlorinated dibenzofurans (PCDFs) are persistent toxic compounds that are ubiquitous in the environment. Nanocomposites of titanium(IV) oxide-vanadium(III) oxide (Ti3V2O7) and titanium(IV) oxide-silicon dioxide (Ti2Si7O30) were prepared and spectroscopically analyzed as potential decontaminants for dioxin-like materials. The analysis confirmed a homogeneous morphology with nanoscale particle size. The Ti-Si sample was found to have a high surface area compared to the Ti-V composite. Vanadium(III) oxide (V2O5) and silicon dioxide (SiO2) were chosen as materials for the formation of heterogeneous compounds with titanium(IV) oxide (TiO2) because they possess a suitable band alignment with TiO2, thus forming effective photocatalysts. This study evaluated the photodegradation of 2,3,7,8-tetrachlorodibenzo-furan (TCDF) in the presence of Ti-Si and Ti-V oxide composites, which was tested using high- (254 nm) and midenergy (302 nm) UV irradiation sources. While Ti-Si showed success in the photodegradation of 2,3,7,8-TCDF dissolved in a (1:1) methanol-tetrahydrofuran (MeOH-THF) solution, the Ti-V composite proved to be a powerful material in adsorbing TCDF with a high capacity immediately upon mixing. Ti-Si oxide was found to decompose TCDF under the two irradiation sources with 98-99% degradation occurring after 70 min. The use of 254 nm as an irradiation source in the presence of Ti-Si was 4.3 times faster than the analogue reaction irradiated without a catalyst. Byproducts of the degradation were evaluated using gas chromatography-mass spectrometry (GC-MS), resulting in a lower chlorinated congener and less toxicity, as the main degradation product.

Fragmentation and release of pristine and functionalized carbon nanotubes from epoxy-nanocomposites during accelerated weathering.

There is an increasing volume of nano-enabled materials in the market. Once composites containing nano-additives are disposed of, weathering could deteriorate their structures, releasing nanoparticles and risking exposure of humans and aquatic organisms. Composite degradation due to environmental aging continues, including structural deterioration resulting in cracking, fragmentation, and release of microplastics and nano-additives to the environment. This research aims to study the degradation and release of initially embedded nanomaterials (NMs) from composites and their toxicity. The molecular interaction of carbon nanotube (CNT)/polymer composites is critical for modifying the polymer properties. This study investigated the interactions of functional multiwalled carbon nanotube (MWCNT) composites which affect their release during accelerated weathering processes. Different epoxy-MWCNT composites were prepared by filling a polymer with pure MWCNTs and MWCNTs functionalized with acid (-COOH) and amine (-NH2) groups. The physical and chemical changes of aged composites were characterized by gravimetric analysis, contact angle measurements, FTIR, SEM, and laser confocal microscopy. A loss of hydrophobicity was observed for composite surfaces long before surface cracks materialized. Released polymer fragments and nanoparticles were analyzed in wash water using TEM, FTIR and Raman spectroscopy. The environmental risks for long-term use of CNT-polymer composites and the influence of fillers on the extent of chemical photodegradation depended on the combination of polymer and fillers. If nanoparticles are released from the matrix, the high surface-to-volume ratio and reactivity of NMs make them highly dynamic in environmental systems. Exposure to these released NMs could negatively affect human health and the environment. This study provides fragmentation and CNT particle release data that could describe how molecular-level interactions between functionalized CNTs and epoxy polymers affect the aging and release of CNTs. A toxicity assessment based on a reactive oxygen species (ROS) formation assay and MTS assay for cell viability and activity of the released polymer and CNT fragments and leachate showed moderate levels of cytotoxicity of released materials as compared to pristine epoxy plates.

Bi-functional photocatalytic heterostructures combining titania thin films with carbon quantum dots (C-QDs/TiO2) for effective elimination of water pollutants.

In this study, carbon quantum dots (C-QDs), prepared via hydrothermal-microwave procedures, were successfully combined with nanostructured titania (TiO2). The photocatalytic oxidation/reduction activity of the C-QDs/TiO2 composite films was evaluated in the decomposition of organic-inorganic contaminants from aqueous solutions under UV illumination. Physicochemical characterizations were applied to investigate the crystal structure of the carbon quantum dots and the composites. It was found that the prepared C-QDs/TiO2 composites had great contribution to the photocatalytic reduction of hexavalent chromium (Cr+6) species and 4-Nitrophenol (PNP) as well as to the photocatalytic oxidation of methylene blue (MB) and Rhodamine B (RhB) dyes. The mechanism of the photocatalytic reaction was studied with trapping experiments, revealing that the electron (e-) radical species were powerfully supported for the photocatalytic reduction of Cr+6 and PNP and the holes (h+) are the main active species for the photocatalytic oxidation reactions.

Pretreatment methods for monitoring microplastics in soil and freshwater sediment samples: A comprehensive review.

This paper reviews the currently used pretreatment methods for microplastics (MPs) analysis in soil and freshwater sediments, primarily sample processing, pretreatment, and characterization methods for MPs analysis. In addition, analytical tools (e.g., lab instruments), MPs characteristics, and MPs quantity, are included in this review. Prior to pretreatment, soil and sediment samples are typically processed using sieving and drying methods, and a sample quantity of <50 g was mostly used for the pretreatment. Density separation was commonly performed before organic matter removal. Sodium chloride (NaCl) and zinc chloride (ZnCl2) were most often used for density separation, and hydrogen peroxide (H2O2) oxidation was most frequently used to remove organic matter. Although advantages of each pretreatment method have been investigated, it is still challenging to determine a universal pretreatment method due to sample variability (e.g., sample characteristics). Furthermore, it is highly required to establish standard pretreatment methods that can be used for various environmental matrices, including air, water, and wastes as well as soil and sediment.

Correlation notice on the electrochemical dealloying and antibacterial properties of gold-silver alloy nanoparticles.

Galvanic replacement reaction was used in the synthesis of bimetallic gold-silver alloy nanoparticles (Au-Ag NPs), where pre-synthesized Ag nanoparticles-polyvinylpyrrolidone (AgNPs-PVP) were used to reduce the aryldiazonium tetrachloroaurate(III) salt in water. TEM images and EDS elemental analysis showed the formation of spherical Au-Ag NPs with sizes of 12.8 ± 4.9 nm and 25.6 ± 14.4 nm for corresponding Au-Ag ratios and termed as Au0.91Ag0.09 and Au0.79Ag0.21, respectively, with different concentrations of the gold precursor. The hydrodynamic sizes measured using dynamic light scattering are 46.4 nm and 74.8 nm with corresponding zeta potentials of - 44.56 and - 25.09 mV in water, for Au0.91Ag0.09 and Au0.79Ag0.21 respectively. Oxidative leachability of Ag ion studies from the starting AgNPs-PVP in 1 M NaCl showed a significant decrease in the plasmon peak after 8 h, indicating the complete dissolution of Ag ions, however, there is enhanced oxidation resistivity of Ag from Au-Ag NPs even after 24 h. Electrochemical studies on glassy carbon electrodes displayed a low oxidation peak in aqueous solutions of 20 mM KCl at 0.16 V and KNO3 at 0.33 V vs. saturated calomel electrode (SCE). We studied the antibacterial activity of Au-Ag alloy nanoparticles against gram-positive Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, and gram-negative Escherichia coli, Salmonella typhimurium, and Pseudomonas aeruginosa. Our findings demonstrated superior antibacterial activity of Au-Ag NPs compared with AgNPs-PVP. Moreover, the nanoparticles inhibited the S. epidermidis biofilm formation.

Degradation of highly chlorinated pesticide, lindane, in water using UV/persulfate: kinetics and mechanism, toxicity evaluation, and synergism by H2O2.

Sulfate radical-advanced oxidation processes (SR-AOPs) are emerging technologies for decomposing organic pollutants in water. This study investigated the efficiency of UV/persulfate (UV/S2O82-) process to degrade lindane in water, showing 93.2% lindane removal ([lindane]0 = 3.43 µM, [S2O82-]0 = 100 µM) at a UV fluence of 720 mJ/cm2. The lindane degradation followed first order kinetics and mechanistic studies suggested H-abstraction by SO4•- and Cl removal via C-Cl bond cleavage by UV-C light. Toxicity assessment using ECOSAR program showed toxicity gradually decreased and eventually no significant toxicity remained when all by-products vanished at high UV dose. Removal efficiency of lindane decreased from 93.2% to 38.4, 45.5, 56.0, 84.3 and 88.6%, by adding 1.0 mg/L humic acid or 1.0 mM CO32-, HCO3-, Cl- or SO42-, respectively. Coupling of H2O2 with UV/S2O82- showed a significant synergistic effect with 99.0% lindane removal at a UV fluence of 600 mJ/cm2, using [S2O82-]0 = [H2O2]0 = 50 µM while UV/H2O2 resulted in only 36.6% lindane removal ([lindane]0 = 3.43 µM, [H2O2]0 = 100 µM) at a UV fluence of 720 mJ/cm2. The results indicate that SR-AOP has potential for consideration as a remedial technology to treat persistent chlorinated pesticides such as lindane in contaminated water.

Monitoring of Anthracene Using Nanoscale Au-Cu Bimetallic Alloy Nanoparticles Synthesized with Various Compositions.

Bimetallic alloy Au-Cu nanoparticles (Au-Cu alloy NPs) were synthesized using a chemical reduction method for sensing applications. Electronic absorption spectroscopy (UV-visible spectroscopy), X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used for the confirmation and morphological studies of the synthesized nanoparticles. The composition of Au-Cu alloy NPs was studied by energy-dispersive spectroscopy (EDS). The high crystallinity of Au-Cu alloy NPs was demonstrated by XRD analysis. Both XRD and SEM analyses revealed that the nanoparticles' size ranges from 15 to 25 nm. Pyrrole was polymerized into polypyrrole (PPy) over a neat and clean glassy carbon electrode (GCE) by potentiodynamic polymerization. The sensitivity of GCE was improved by modifying it into a composite electrode. The composite electrode was developed by coating GCE with an overoxidized PPy polymer followed by Au-Cu alloy NPs. The ratio of Au and Cu was carefully controlled. The composite electrode (PPyox/Au-Cu/GCE) successfully detected an environmental toxin anthracene with a detection limit of 0.15 µM, as evidenced by cyclic voltammetry (CV), square-wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS).

Protein-Coated Aryl Modified Gold Nanoparticles for Cellular Uptake Study by Osteosarcoma Cancer Cells.

Gold nanoparticles coated with proteins have shown extraordinary biocompatibility which advanced to several nanomedicine engineering applications. We synthesized protein-coated gold nanoparticles using green and chemical reduction routes for cellular uptake study. In the current work, we coated gold-aryl nanoparticles of the type AuNPs-C6H4-4-COOH with bovine serum albumin (BSA), collagen, zein, and lysozyme proteins. Both routes were carried out without phase-transfer catalysts or extraneous stabilizing agents. High crystallinity of the AuNPs synthesized by the green route can be seen in transmission electron microscopy images. Osteosarcoma cancer cells are malignant bone tumors with abnormal cellular functions. Studies using MG-63 cells will provide mechanistic suggestions on the details of the amplification in tumors. We studied the cellular uptake of the bioconjugates by MG-63 osteosarcoma cells using laser confocal fluorescence microscopy (LCFM) and flow cytometry. In the LCFM study, BSA-AuNPs were uptaken most efficiently of all protein-coated gold nanoparticles synthesized by the green route. Lysozyme-AuNPs synthesized by the chemical reduction method were mostly efficiently internalized by MG-63 cells among all AuNPs. Zein- and lysozyme-coated AuNPs, though of relatively small size, prepared by the green method were not efficiently uptaken by MG-63. The two nanoparticles are negatively charged, and zein is also a hydrophobic coat. The difference in hydrophobicity and charge might have affected the internalization. All of those coated nanoparticles that were efficiently uptaken can potentially be used as diagnostic and therapeutic agents for osteosarcoma.

Efficient synthesis of amino acids capped gold nanoparticles from easily reducible aryldiazonium tetrachloroaurate(III) salts for cellular uptake study.

Biomimetic synthesis of gold nanoparticles (GNPs) is critical in biomedical applications. Gold bioconjugates were fabricated by capping the water-dispersible gold-carbon nanoparticles with tyrosine, tryptophan and cysteine amino acids. Incubation of the water-soluble and easily reducible aryldiazonium gold(III) salt [HOOC-4-C6H4N≡N]AuCl4 with amino acids at room temperature formed a purple color over a few minutes with tryptophan and tyrosine and over two hours with cysteine. Rarely that cysteine is capable of reducing gold(III) precursors; however, a cysteine capped gold bioconjugate was synthesized and characterized in this study. Capping GNPs with amino acids was confirmed by high resolution transmission electron microscopy (TEM) and agarose gel electrophoresis. Depending on the amino acid, synthesized particles size was 27.2 ± 5.4 nm, 14.6 ± 7.7 nm and 8.6 ± 2.6 nm for tyrosine, tryptophan and cysteine, respectively. The amino acids capped GNPs showed negligible cytotoxicity to human dermal normal fibroblast cell lines. The highly water dispersible bioconjugates were studied for in vitro cellular uptake by HeLa cancer cells using confocal laser scan microscopy (CLSM) after being labelled with FITC (GNPs-COOH-FITC) and the nuclei were counter stained with DAPI fluorescent dyes. The biomimetic route for the synthesis of the amino acids reduced gold-carbon nanoparticles will benefit the applications in biomedical devices and biosensors.

Role of water chemistry on stability, aggregation, and dissolution of uncoated and carbon-coated copper nanoparticles.

Intentional or accidental release of copper nanoparticles (Cu-NPs) from consumer products during manufacturing, use, and end-of-life management could pose health and ecological risks. This paper presents a detailed study on the role of water chemistry on the fate of uncoated and carbon-coated Cu-NPs dispersed in aqueous cetyltrimethylammonium bromide (CTAB) surfactant in the presence and absence of humic acids (HAs). A range of water chemistry and HAs had minimum impact on hydrodynamic diameter and zeta-potential values of uncoated and carbon-coated Cu-NPs. The water pH significantly (p < 0.001) affected the aggregation of uncoated Cu-NPs unlike that of carbon-coated Cu-NPs; however, the presence of HAs increased the stability of uncoated Cu-NPs. Although CTAB is considered as an efficient dispersant to stabilize Cu-NPs, the effect descended with time for uncoated Cu-NPs. The dissolution of Cu over time decreased with increasing pH for both uncoated (0.5-50% weight) and carbon-coated (0.5-40% weight) Cu-NPs. However, carbon-coated Cu-NPs exhibited significant dissolution (p < 0.001) at neutral pH than uncoated Cu-NPs may be due to the additional carbon it acquired during coating. Increasing HAs concentration from 0 to 15 mg L-1 at pH 5.5 inhibited aggregations but enhanced dissolution of the uncoated and carbon-coated Cu-NPs. These findings inform risk analysis of Cu-NPs including how Cu-NPs fate, mobility and bioavailability are modulated by particles coating and dispersant, HAs presence, water chemistry and exposure time in dispersion media.

Environmentally friendly synthesized and magnetically recoverable designed ferrite photo-catalysts for wastewater treatment applications.

Fenton processes are promising wastewater treatment alternatives for bio-recalcitrant compounds. Three different methods (i.e., reverse microemulsion, sol-gel, and combustion) were designed to synthesize environmentally friendly ferrites as magnetically recoverable catalysts to be applied for the decomposition of two pharmaceuticals (ciprofloxacin and carbamazepine) that are frequently detected in water bodies. The catalysts were used in a heterogeneous solar photo-Fenton treatment to save the cost of applying high-energy UV radiation sources, and was performed under a slightly basic pH to avoid metal leaching and adding salts for pH adjustment. All the developed catalysts resulted in the effective treatment of ciprofloxacin and carbamazepine in both synthetic and real domestic wastewater. In particular, the sol-gel synthesized ferrite was more magnetic and more suitable for reuse. The degradation pathways of both compounds were elucidated for this treatment. The degradation of ciprofloxacin involved attacks to the quinolone and piperazine rings. The degradation pathway of carbamazepine involved the formation of hydroxyl carbamazepine and dihydroxy carbamazepine before yielding acridine by hydrogen abstraction, decarboxylation, and amine cleavage, which would be further oxidized.

Influence of water chemistry on colloid-size Cu-based pesticides particles: A case of Cu(OH)2 commercial fungicide/bactericide.

The intensive, widespread, and ever-increasing applications of Cu-based pesticides in agriculture could potentially increase environmental exposures via different routes. Unlike ionic/bulk forms, the fate, transport, and toxicity of colloid-size Cu-based pesticides are not well studied. This paper provides evaluation outcomes of granule and dispersion characterizations, stability, and dissolution of colloid-size particles of Cu(OH)2 commercial pesticide product at a range of water chemistry. The evaluated product contained about 35% weight of metallic Cu equivalent and Cu(OH)2 particles with sizes < 1 µm of which a fraction of nanoscale particles exist. The presence of Ca2+ at ionic strengths of >0.01 M and 0.001-0.2 M significantly influenced (p < 0.001) particle size (PS) and ζ-potential values, respectively at all investigated pH values. Cu dissolution at pH 5.5 was significant (p < 0.001) and exceeded Cu dissolutions at pH 7.0 by 87-90% and at pH 8.5 by 87-95% in all dispersions. The order of Cu dissolution was pH 5.5 > pH 7.0 > pH 8.5 in all dispersions. Cu dissolution was relatively reduced by 53% by increasing HA from 0 to 5 mg L-1 and enhanced by 55% by increasing HA from 5 to 15 mg L-1, however, the overall Cu dissolution was decreased by 27% by increasing HA from 0 to 15 mg L-1. Thus, HAs reduced the dissolution of Cu at pH < 7. The findings provide an insight into how water chemistry influences the fate and transport of colloid-size Cu-based pesticides particles.

Fragmentation of polymer nanocomposites: modulation by dry and wet weathering, fractionation, and nanomaterial filler.

In recent years, an increasing number of polymeric composites incorporating engineered nanomaterials (ENMs) have reached the market. Such nano-enabled products (NEPs) present enhanced performance through improved mechanical, thermal, UV protection, electrical, and gas barrier properties. However, little is known about how environmental weathering impacts ENM release, especially for high-tonnage NEPs like kaolin products, which have not been extensively examined by the scientific community. Here we study the simulated environmental weathering of different polymeric nanocomposites (epoxy, polyamide, polypropylene) filled with organic (multiwalled carbon nanotube, graphene, carbon black) and inorganic (WS2, SiO2, kaolin, Fe2O3, Cu-phthalocyanines) ENMs. Multiple techniques were employed by researchers at three laboratories to extensively evaluate the effect of weathering: ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), optical microscopy, contact angle measurements, gravimetric analysis, analytical ultracentrifugation (AUC), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy. This work aimed to elucidate the extent to which weathering protocol (i.e. wet vs. dry) and diverse filler characteristics modulate fragment release and polymer matrix degradation. In doing so, it expanded the established NanoRelease protocol, previously used for analyzing fragment emission, by evaluating two significant additions: (1) simulated weathering with rain events and (2) fractionation of sample leachate prior to analysis. Comparing different composite materials and protocols demonstrated that the polymer matrix is the most significant factor in NEP aging. Wet weathering is more realistic than dry weathering, but dry weathering seems to provide a more controlled release of material over wet. Wet weathering studies could be complicated by leaching, and the addition of a fractionation step can improve the quality of UV-vis measurements.

Green and cytocompatible carboxyl modified gold-lysozyme nanoantibacterial for combating multidrug-resistant superbugs.

The dissemination of multi-drug resistant (MDR) superbugs in hospital environments, communities and food animals and the very dynamic bacterial mutation frequency require the development of prolonged therapeutic strategies to gain mastery over antibiotic resistance. A AuNP-lysozyme nanoantibacterial was fabricated by the conjugation of AuNPs-C6H4-4-COOH with lysozyme via green reduction of aryldiazonium gold(iii) salt [HOOC-4-C6H4N[triple bond, length as m-dash]N]AuCl4. Results from molecular docking calculations aimed at revealing the binding mode of benzoic acid with the lysozyme structure clearly showed the lowest energy conformation with benzoic acid bound in the deep buried hydrophobic cavity of the protein active site through strong hydrogen bonding and hydrophobic interactions, thus validating the experimental outcomes of the current study which also exhibited the binding of -COOH functional groups in the interior of the protein structure. The superiority of the lysozyme bioconjugate against superbugs was demonstrated by the enhanced and broadened lysozyme antibacterial activities of 98-99% against extended spectrum beta lactamase (ESBL) producing Escherichia coli and imipenem-resistant Pseudomonas aeruginosa clinical isolates and a selection of Gram-negative and Gram-positive standard ATCC strains. Selective toxicity against bacteria was confirmed by the high viability of HeLa and fibroblast cell lines and the outstanding hemocompatibility at the minimum bacterial inhibitory concentrations (MICs). Turbidimetric enzyme kinetic assay showed the enhancement of the lysozyme hydrolytic activity by gold nanoparticles on the Micrococcus lysodeikticus bacterial substrate. Using gel electrophoresis, the induced cell wall breakdown was confirmed by detecting the leaked-out bacterial genomic DNA. The integrity and morphology changes of the E. coli bacteria were investigated using a scanning electron microscope after one hour of contact with the lysozyme-gold bioconjugate. The antibacterial functionalities showed little or no damage to healthy human cells and can be applied to wound dressings and medical devices.

Characterization of colloid-size copper-based pesticide and its potential ecological implications.

The intensive use of Cu-based pesticides in agriculture could have an unintended impact on the ecosystems and human health via different exposure pathways. This paper presents the results of experiments involving colloidal stability, aggregation, and dissolution of Cu2O commercial pesticide under various environmental conditions in view of ecological implications. The investigated pesticide contains ∼750 g kg-1 Cu (75% weight of product), Cu2O particles with sizes < 1 µm, and nominal size fraction of Cu2O nanoparticles. The co-presence of Ca2+ (20 mM) and humic acid (HA, 15 mg L-1) significantly modulates (p < 0.001) the colloidal stability and mobility of particles. The dissolution of Cu at pH 5.5 was about 85%, 90%, and 75% weight more than the dissolution of Cu at pH 7.0, pH 8.5, and pH 7.0 and pH 8.5 combined, respectively in all dispersions. However, increasing HA content from 0 to 15 mg L-1 reduced the dissolution of Cu by 56%, 50%, and 40% weight at pH 5.5, 7.0, and 8.5, respectively. Thus, pH below 7.0 is a critical factor to control the dissolution and bioavailability of Cu that may pose ecotoxicity and environmental pollution, whereas pH above 7.0 and the presence of HA attenuate the pH effect. These findings provide insight into how the potential mobility and bioavailability of Cu is modulated by the water chemistry under various environmental scenarios and media.

Treatment of reverse osmosis concentrate using an algal-based MBR combined with ozone pretreatment.

Algal treatment was combined with ozone pretreatment for treatment of synthetic reverse osmosis concentrate (ROC) prior to microfiltration. The research mainly focused on minimizing the fouling of polyvinylidene-fluoride membranes and maximizing the restoration of membrane permeability. The algal treatment alone was only moderately effective for the mitigation of fouling in microfiltration, while a markedly improved performance was achieved when the algal treatment followed ozonation. The combination of ozonation and algal treatment reduced membrane permeability decline and significantly (p < 0.05) increased the reversibility of fouling after hydraulic washing. A longitudinal evaluation was also performed with a goal of achieving a robust removal of contaminants. Ozonation followed by algal treatment was very effective in attenuating both caffeine and carbamazepine, as well as removing organic matter and inorganic nutrients from ROC in a single bioreactor. In this study, an alkaline condition (∼pH 12), produced by microalgae in the light without supplemental aeration was applied for in-situ cleaning of fouled membranes. The result showed that the algal-induced cleaning successfully restored the permeability of organic-fouled membranes during the filtration of both raw and algal-treated ROC. This in-situ strategy offers a novel option for periodic cleaning of fouled membranes while maintaining operational simplicity, especially for existing submerged membrane filtration facilities.

Polypropylene-MWCNT composite degradation, release, detection, and toxicity of MWCNT during accelerated aging.

Nanomaterials (NM) are incorporated into polymers to enhance their properties. However, there are a limited number of studies on the aging of these nanocomposites and the resulting potential release of NM. To characterize NM at critical points in their life cycles, polypropylene (PP) and multiwall carbon nanotube filled PP (PP-MWCNT) plates with different thicknesses (from 0.25 mm to 2 mm) underwent accelerated weathering in a chamber that simulates solar irradiation and rainfall. The physicochemical changes of the plates depended on the radiation exposure, the plate thickness, and the presence of CNT fillers. Photodegradation increased with aging time, making the exposed surface more hydrophilic, decreasing the surface hardness and creating surface stress-cracks. Aged surface and cross-section showed crazing due to the polymer bond scission and the formation of carbonyls. The degradation was higher near the UV-exposed surface as the intensity of the radiation and oxygen diffusion decreased with increasing depth of the plates, resulting in an oxidation layer directly proportional to oxygen diffusion. Thus, sample thickness determines the kinetics of the degradation reaction and the transport of reactive species. Plastic fragments, which are less than 1 mm, and free CNTs were released from weathered MWCNT-PP. The concentrations of released NM that were estimated using ICP-MS, increased with prolonged aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability, were performed on the released CNTs. The toxicity of the released fragments and CNTs to A594 adenocarcinomic human alveolar basal epithelial cells was observed. The released polymer fragments and CNTs did not show significant toxicity under the experimental conditions in this study. This study will help manufacturers, users of consumer products with nanocomposites and policymakers in the development of testing guidelines, predictive models, and risk assessments and risk based-formulations of NM exposure.

Evaluating Weathering of Food Packaging Polyethylene-Nano-clay Composites: Release of Nanoparticles and their Impacts.

Nano-fillers are increasingly incorporated into polymeric materials to improve the mechanical, barrier or other matrix properties of nanocomposites used for consumer and industrial applications. However, over the life cycle, these nanocomposites could degrade due to exposure to environmental conditions, resulting in the release of embedded nanomaterials from the polymer matrix into the environment. This paper presents a rigorous study on the degradation and the release of nanomaterials from food packaging composites. Films of nano-clay-loaded low-density polyethylene (LDPE) composite for food packaging applications were prepared with the spherilene technology and exposed to accelerated weathering of ultraviolet (UV) irradiation or low concentration of ozone at 40 °C. The changes in the structural, surface morphology, chemical and physical properties of the films during accelerated weathering were investigated. Qualitative and quantitative changes in properties of pristine and aged materials and the release of nano-clay proceeded slowly until 130 hr irradiation and then accelerated afterward resulting complete degradation. Although nano-clay increased the stability of LDPE and improved thermal and barrier properties, they accelerated the UV oxidation of LDPE. With increasing exposure to UV, the surface roughness, chemiluminescence index, and carbonyl index of the samples increased while decreasing the intensity of the wide-angle X-ray diffraction pattern. Nano-clay particles with sizes ranging from 2-8 nm were released from UV and ozone weathered composite. The concentrations of released nanoparticles increased with an increase in aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability were also performed on the released nano-clay and clay polymer. The released nano-clays basically did not show toxicity. Our combined results demonstrated the degradation properties of nano-clay particle-embedded LDPE composites toxicity of released nano-clay particles to A594 adenocarcinomic human alveolar basal epithelial cells was observed, which will help with future risk based-formulations of exposure.

Environmental aging and degradation of multiwalled carbon nanotube reinforced polypropylene.

The degradation of polypropylene (PP) and PP-multiwalled carbon nanotube (PP-MWCNT) panels during environmental weathering resulted in an increased degree of crystallinity, making them brittle, and creating surface cracks. The degradation led to a breakdown of the panels and increased the potential for nanorelease. Thermal analysis revealed that the thickness of the test panels and reinforcement with MWCNTs had a significant influence on the stability of PP-MWCNT composites. Differential scanning calorimetry indicated that the MWCNTs acted as nucleation points, increasing the crystallization temperatures of PP-MWCNT, which reduced the extent of aging. Weathering decreased both the melting and crystallization temperatures of PP by as much as 20 o C. The reduction in the temperatures was inversely proportional to the thickness of the panels. The activation energy (E a ) obtained using isoconversional kinetics of the TGA analysis showed that the effective thermo-oxidative degradations of PP changed during aging. The E a for the initial stages of thermal degradation decreased from ~330 kJ/mol to ~100 kJ/mol for aged PP. During the late degradation stages, the E a values increased to ~300 kJ/mol. These results suggest that early degradation were altered because of the changes in the molecular structure of the aged P and a shift in the degradation rate-limiting steps.