Estimation of the atmospheric flux of nutrients and trace metals to the Eastern Tropical North Atlantic Ocean

Atmospheric deposition contributes potentially significant amounts of the nutrients iron, nitrogen and phosphorus (via mineral dust and anthropogenic aerosols) to the oligotrophic tropical North Atlantic Ocean. Transport pathways, deposition processes and source strengths contributing to this atmospheric flux are all highly variable in space and time. Atmospheric sampling was conducted during 28 research cruises through the Eastern Tropical North Atlantic (ETNA) over a 12 year period and a substantial dataset of measured concentrations of nutrients and trace metals in aerosol and rainfall over the region was acquired. This database was used to quantify (on a spatial- and seasonal-basis) the atmospheric input of ammonium, nitrate, soluble phosphorus and soluble and total iron, aluminium and manganese to the ETNA. The magnitude of atmospheric input varies strongly across the region, with high rainfall rates associated with the Inter-tropical Convergence Zone contributing to high wet deposition fluxes in the south, particularly for soluble species. Dry deposition fluxes of species associated with mineral dust exhibited strong seasonality, with highest fluxes associated with winter-time low-level transport of Saharan dust. Overall (wet plus dry) atmospheric inputs of soluble and total trace metals were used to estimate their soluble fractions. These also varied with season and were generally lower in the dry north than in the wet south. The ratio of ammonium plus nitrate to soluble iron in deposition to the ETNA was lower than the N:Fe requirement for algal growth in all cases, indicating the importance of the atmosphere as a source of excess iron

Isothermal calorimetry protocols to monitor the shelf life and aftermarket follow-up of fresh cut vegetables

Protocols and guidelines were assessed in order to apply isothermal calorimetry as a complementary/alternative method to monitoring, during the shelf life and the microbial growth/metabolism in commercial fresh cut vegetables with random initial microbial population. Moreover, the endogenous microbial population was used as a biosensor to check the modifications occurred during long storage for aftermarket characterization in the frame of vegetable waste treatments. Validation was obtained following ready-to-use carrots highlighting the effects of the different exposed surfaces (cylinders, sticks and a`-la-julienne cut) on the overall spoiling process during shelf life and green salad stored up to 14 days with regard to the aftermarket characterization

Oxidation and Cross-Linking in the Curing of Air-Drying Artists' Oil Paints

In this study, the chemistry of air-drying artist's oil paint curing and aging up to 24 months was studied. The objective is to improve our molecular understating of the processes that lead to the conversion of the fluid binder into a dry film and how this evolves with time, which is at the base of a better comprehension of degradation phenomena of oil paintings and relevant to the artists' paint manufacturing industry. To this aim, a methodological approach based on thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), gas chromatography-mass spectrometry (GC-MS), and analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS) was implemented. Model paintings based on linseed oil and safflower oil (a drying and a semidrying oil, respectively) mixed with two historically relevant pigments - lead white (a through drier) and synthetic ultramarine blue (a pigment often encountered in degraded painting layers) - were investigated. The oil curing under accelerated conditions (80 °C under air flow) was followed by isothermal TG analysis. The oxygen uptake profiles were fit by a semiempiric equation that allowed to study the kinetics of the oil oxidation and estimate oxidative degradation. The DSC signal due to hydroperoxide decomposition and radical recombination was used to monitor the radical activity over time and to evaluate the stability of peroxides formed in the paint layers. GC-MS was performed at 7 and 24 months of natural aging to investigate the noncovalently cross-linked fractions and Py-GC-MS to characterize the whole organic fraction of the model paintings, including the cross-linked network. We show that the oil-pigment combination may have a strong influence on the relative degree of oxidation of the films formed with respect to its degree of cross-linking, which may be correlated with the literature on the stability of painting layers. Undocumented pathways of oxidation are also highlighted

Valorization of not soluble byproducts deriving from green keratin extraction from poultry feathers as filler for biocomposites

The valorization of poultry feathers wastes is very important to reduce the environmental pollution deriving from their disposal. In this frame, we present the production process of completely natural, biodegradable, biocompatible, and eco-friendly composites made by not soluble keratin (NSK) and poly(lactic acid) (PLA). NSK has been obtained as a byproduct of a microwave-assisted keratin extraction from poultry feathers and it has been added to PLA pellets without adding any additional compatibilizers or plasticizers, unlike from the other works reported in the literature until now. The mixture has been used to obtain homogeneous NSK-based PLA filaments by means of hot-melt extrusion technology. The filaments have been subsequently 3D printed to explore applications in the additive manufacturing field. All the samples have unaltered thermal stability, but reduced toughness with respect to neat PLA. Other tested parameters (water adsorption, glass transition, and crystallinity) are dependent on NSK content and fabrication technology. Besides, Fourier Transform Infrared Spectroscopy highlights the differences in the structure of the NSK-based PLA filaments and 3D printed samples

The DSC monitoring of oil melting to follow the oil curing

The drying of an oil paint is due to the polyunsaturations of the oil in the binder. Polyunsaturated oils dry trough an autoxidation process in which the double bonds of linolenic and linoleic acids naturally react with the oxygen present in the atmosphere. The gradual conversion of the liquid oil through a soft gel to a rubbery solid occurs as a result of a multistep free radical chain reaction. During the propagation step, hydroperoxides are formed. A method frequently used to follow the oil curing is the DSC monitoring of the peroxide decomposition peak during time. Since the oil polymerization affects its crystallinity, we propose here an altemative method to asses the oil curing. The melting peak of linseed oil samples is measured at different times of curing and compared with the pro\ufb01le of the peroxide decomposition peak over time. The comparison shows that the two phenomena are strongly correlated and that, when the maximum of the peroxide content is reached, the melting peak disappears. The study of the DSC melting peak is therefore proposed as a valid alternative tool to monitor the curing of an oil paint

Microwave-assisted in situ laser dye incorporation into high sensitivity whispering gallery mode microresonators

Optical whispering gallery mode microresonators (WGM-μRs) are powerful sensitive components with many analytical applications. Here, spherical WGM-μRs have been synthesised in a single-step microwave (MW)-assisted heterophase polymerisation. The microresonators are based on poly(styrene) beads into which the organic lasing dye nile red was incorporated as gain medium in situ during the polymerisation. The particle diameter and diameter distribution of the synthesised particles were tuned in the range of around 200 nm up to 50 μm by adjusting the concentration between stabiliser poly-(N-vinyl pyrrolidone) (PVP) and monomer styrene, and the solvent composition in the dispersion process. Lower water content enabled the synthesis of spherical particles with large size polydispersity, from which WGM-μRs with a variety of diameters were selected. Microspheres with diameters ≳3.5 μm supported WGMs. The WGMs were excited through free space via the fluorescence of the laser dye. Pumping power levels <1 μW were sufficient to excite WGMs. WGM shifts of beads with diameter between ≈5 and 30 μm measured in air and water show a sensitivity up to 54 nm/RIU for the smallest particles. Dye doped WGM-μR in the low μm size range obtained by the MW-assisted polymerisation process with its versatility, low processing times and high yields opens new horizons for the applications of these systems as sensors

Modeling of the acute toxicity of benzene derivatives by complementary QSAR methods

A data set containing acute toxicity values (96-h LC50) of 69 substituted benzenes for fathead minnow (Pimephales promelas) was investigated with two Quantitative Structure- Activity Relationship (QSAR) models, either using or not using molecular descriptors, respectively. Recursive Neural Networks (RNN) derive a QSAR by direct treatment of the molecular structure, described through an appropriate graphical tool (variable-size labeled rooted ordered trees) by defining suitable representation rules. The input trees are encoded by an adaptive process able to learn, by tuning its free parameters, from a given set of structureactivity training examples. Owing to the use of a flexible encoding approach, the model is target invariant and does not need a priori definition of molecular descriptors. The results obtained in this study were analyzed together with those of a model based on molecular descriptors, i.e. a Multiple Linear Regression (MLR) model using CROatian MultiRegression selection of descriptors (CROMRsel). The comparison revealed interesting similarities that could lead to the development of a combined approach, exploiting the complementary characteristics of the two approaches

One-pot process: Microwave-assisted keratin extraction and direct electrospinning to obtain keratin-based bioplastic

Poultry feathers are among the most abundant and polluting keratin-rich waste bio-masses. In this work, we developed a one-pot microwave-assisted process for eco-friendly keratin extraction from poultry feathers followed by a direct electrospinning (ES) of the raw extract, without further purification, to obtain keratin-based bioplastics. This microwave-assisted keratin extraction (MAE) was conducted in acetic acid 70% v/v. The effects of extraction time, solvent/feathers ratio, and heating mode (MAE vs conventional heating) on the extraction yield were investigated. The highest keratin yield (26 ± 1% w/w with respect to initial feathers) was obtained after 5 h of MAE. Waste-derived keratin were blended with gelatin to fabricate keratin-based biodegradable and bio-compatible bioplastics via ES, using 3-(Glycidyloxypropyl)trimethoxysilane (GPTMS) as a cross-linking agent. A full characterization of their thermal, mechanical, and barrier properties was performed by differential scanning calorimetry, thermogravimetric analysis, uniaxial tensile tests, and water permeability measurements. Their morphology and protein structure were investigated using scanning electron microscopy and attenuated total reflection-infrared spectroscopy. All these characterizations highlighted that the properties of the keratin-based bioplastics can be modulated by changing keratin and GPTMS concentrations. These bioplastics could be applied in areas such as bio-packaging and filtration/purification membranes

Hexavalent chromium release over time from a pyrolyzed Cr-bearing tannery sludge

Pyrolysis in an inert atmosphere is a widely applied route to convert tannery wastes into reusable materials. In the present study, the Cr(III) conversion into the toxic hexavalent form in the pyrolyzed tannery waste referred to as KEU was investigated. Ageing experiments and leaching tests demonstrated that the Cr(III)–Cr(VI) inter-conversion occurs in the presence of air at ambient temperature, enhanced by wet environmental conditions. Microstructural analysis revealed that the Cr-primary mineral assemblage formed during pyrolysis (Cr-bearing srebrodolskite and Cr-magnetite spinel) destabilized upon spray water cooling in the last stage of the process. In the evolution from the higher to the lower temperature mineralogy, Cr is incorporated into newly formed CrOOH flakes which likely react in air forming extractable Cr(VI) species. This property transforms KEU from an inert waste to a hazardous material when exposed to ordinary ambient conditions

Evaluation of thermal stability of model protein-polymer conjugates

Protein-polymer conjugates are a new trend in biomedical chemistry for the treatment of several diseases. The design of novel and efficient conjugates, as well a deeper understanding of the conjugate structure and its behaviour in solution has much academic and industry potential. Here, we present a calorimetric study on the role of the "gold standard" poly(ethylene glycol) (PEG) in some model bioconjugates, followed by the synthesis and evaluation of conjugates made with a new class of biocompatible and biodegradable polymers (PPE, poly(phosphoester)s), promising candidates in the biomedical field to substitute the polymer PEG. The studies on the PEGylated proteins was carried out with nano and micro differential scanning calorimeters, and the evaluation of the thermograms obtained in different conditions have revealed the role of the polymer in preventing the drug aggregation, while at the same time its week interactions with the protein permit to preserve its biological activity. In the second part, after the test of the biocompatibility of the new polymers in simulated stomach fluid and in blood plasma, we have synthesised novel conjugates using PPEs of variable length, while the variation of the lateral group of the polymer is currently under investigation. Overall, the analyses conducted (including activity essay, calorimetry and fluorimetry measurements) show that the covalent attachment of the polymer does not irrevocably affect the protein's features under physiological conditions, suggesting the significant potentialities of this new class of polymers for the design of a new generation of conjugates classes