Deep dive into the chronic toxicity of tyre particle mixtures and their leachates.

Particles from the tread of vehicle tyres are a global pollutant, which are emitted into the environment at an approximate rate of 1.4 kg.year-1 for an average passenger-car. In this study, popular tyre brands were used to generate a tyre tread microparticle mixture. The chronic toxicity of both particles and chemical leachates were compared on a planktonic test species (Daphnia magna). Over 21 days of exposure, pristine tyre tread microparticles were more toxic (LC50 60 mg.L-1) than chemical lechates alone (LC50 542 mg.L-1). Microparticles and leachates showed distinct effects on reproduction and morphological development at environmentally relevant concentrations, with dose-dependent uptake of particles visible in the digestive tract. Chemical characterization of leachates revealed a metal predominance of zinc, titanium, and strontium. Of the numerous organic chemicals present, at least 54 were shared across all 5 tyre brands, with many classified to be very toxic. Our results provide a critically needed information on the toxicity of tyre tread particles and the associated chemicals that leach from them to inform future mitigation measures. We conclude that tyre particles are hazardous pollutants of particular concern that are close to or possibly above chronic environmental safety limits in some locations.

Translocation of 14C-polystyrene nanoplastics into fish during a very-low concentration dietary exposure.

Assessing the dietary accumulation of nanoplastics in animals following very-low exposure concentrations is restricted due to analytical limitations. This study adapted a method for synthesising semi-stable 14C-PS NPs (through styrene polymerisation) in small volumes for deployment in environmental studies. The method was developed with non-labelled material where the final polystyrene product had a primary particle size of 35 ± 8 nm (as measured by transmission electron microscopy). This method was then applied to 14C-labelled styrene to produce radiolabelled polystyrene nanoplastics (14C-PS NPs). The 14C-PS NPs were added (top-dressed) to a commercially available fish feed, with a measured concentration of 27.9 ± 2.1 kBq kg-1 (n = 5), equating to 5.9 µg polystyrene kg-1 feed. Fish (rainbow trout; Oncorhynchus mykiss) were fed this diet at a ration of 2% body weight per day for a period of two weeks. On day 3, 7 and 14, the fish were sampled for the mid intestine, hind intestine, kidney and liver, and measured for tissue radioactivity (determined by liquid scintillation counting). Some background activity was detected in the control samples (e.g., 1-16 and 4-11 Bq g-1 in the hind intestine and liver, respectively) which is due to natural background fluorescence. By the end of the experiment, the hind intestine and liver had significantly elevated radioactivity (25.3 and 15.0 Bq g-1, respectively) compared to the control, indicating the accumulation of nano polystyrene. In the liver, this equated to 1.8 µg polystyrene g-1 dry weight. This study confirms the accumulation of nano particles in vertebrates at low, environmentally relevant concentration, and highlights radiolabelling as a methodological approach suitable for exploring the bioaccumulation of nanoplastics and potential impacts.

Metal-Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al-SBA-15.

Invited for this month's cover is the group of Karen Wilson and Adam Lee at RMIT University. The image shows platinum nanoparticles and Brønsted acid sites working cooperatively to catalyse the efficient hydrodeoxygenation of phenolic lignin residues to produce sustainable biofuels. The Full Paper itself is available at 10.1002/cssc.202000764.

Metal-Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al-SBA-15.

Hydrodeoxygenation (HDO) is a promising technology to upgrade fast pyrolysis bio-oils but it requires active and selective catalysts. Here we explore the synergy between the metal and acid sites in the HDO of anisole, a model pyrolysis bio-oil compound, over mono- and bi-functional Pt/(Al)-SBA-15 catalysts. Ring hydrogenation of anisole to methoxycyclohexane occurs over metal sites and is structure sensitive; it is favored over small (4 nm) Pt nanoparticles, which confer a turnover frequency (TOF) of approximately 2000 h-1 and a methoxycyclohexane selectivity of approximately 90 % at 200 °C and 20 bar H2 ; in contrast, the formation of benzene and the desired cyclohexane product appears to be structure insensitive. The introduction of acidity to the SBA-15 support promotes the demethyoxylation of the methoxycyclohexane intermediate, which increases the selectivity to cyclohexane from 15 to 92 % and the cyclohexane productivity by two orders of magnitude (from 15 to 6500 mmol gPt -1 h-1 ). Optimization of the metal-acid synergy confers an 865-fold increase in the cyclohexane production per gram of Pt and a 28-fold reduction in precious metal loading. These findings demonstrate that tuning the metal-acid synergy provides a strategy to direct complex catalytic reaction networks and minimize precious metal use in the production of bio-fuels.

Tunable Silver-Functionalized Porous Frameworks for Antibacterial Applications.

Healthcare-associated infections and the rise of drug-resistant bacteria pose significant challenges to existing antibiotic therapies. Silver nanocomposites are a promising solution to the current crisis, however their therapeutic application requires improved understanding of underpinning structure-function relationships. A family of chemically and structurally modified mesoporous SBA-15 silicas were synthesized as porous host matrices to tune the physicochemical properties of silver nanoparticles. Physicochemical characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and porosimetry demonstrate that functionalization by a titania monolayer and the incorporation of macroporosity both increase silver nanoparticle dispersion throughout the silica matrix, thereby promoting Ag2CO3 formation and the release of ionic silver in simulated tissue fluid. The Ag2CO3 concentration within functionalized porous architectures is a strong predictor for antibacterial efficacy against a broad spectrum of pathogens, including C. difficile and methicillin-resistant Staphylococcus aureus (MRSA).

Impact of Macroporosity on Catalytic Upgrading of Fast Pyrolysis Bio-Oil by Esterification over Silica Sulfonic Acids.

Fast pyrolysis bio-oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom- and energy-efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid (PrSO3 H) silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA-15 architectures (post-functionalized by hydrothermal saline-promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C3 ) to 110 % (C12 ). Macroporous-mesoporous PrSO3 H/SBA-15 also provides a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast-pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, as determined by GC×GC-time-of-flight mass spectrometry (GC×GC-ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.

Acetic Acid Ketonization over Fe3O4/SiO2 for Pyrolysis Bio-Oil Upgrading.

A family of silica-supported, magnetite nanoparticle catalysts was synthesised and investigated for continuous-flow acetic acid ketonisation as a model pyrolysis bio-oil upgrading reaction. The physico-chemical properties of Fe3O4/SiO2 catalysts were characterised by using high-resolution transmission electron microscopy, X-ray absorption spectroscopy, X-ray photo-electron spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, thermogravimetric analysis and porosimetry. The acid site densities were inversely proportional to the Fe3O4 particle size, although the acid strength and Lewis character were size-invariant, and correlated with the specific activity for the vapour-phase acetic ketonisation to acetone. A constant activation energy (∼110 kJ mol-1), turnover frequency (∼13 h-1) and selectivity to acetone of 60 % were observed for ketonisation across the catalyst series, which implies that Fe3O4 is the principal active component of Red Mud waste.

Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation.

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C = O over C = C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C = O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

Tunable Pt nanocatalysts for the aerobic selox of cinnamyl alcohol.

The selective aerobic oxidation of cinnamyl alcohol over Pt nanoparticles has been tuned via the use of mesoporous silica supports to control their dispersion and oxidation state. High area two-dimensional SBA-15, and three-dimensional, interconnected KIT-6 silica significantly enhance Pt dispersion, and thus surface PtO2 concentration, over that achievable via commercial low surface area silica. Selective oxidation activity scales with Pt dispersion in the order KIT-6 ≥ SBA-15 > SiO2, evidencing surface PtO2 as the active site for cinnamyl alcohol selox to cinnamaldehyde. Kinetic mapping has quantified key reaction pathways, and the importance of high O2 partial pressures for cinnamaldehyde production.