Calcium phosphates from fish bones in sunscreen: An LCA and toxicity study of an emerging material for circular economy.

The use of sustainable and natural materials is an ever-increasing trend in cosmetic. Natural calcium phosphate (CaP-N) from food by-products and especially from fisheries (i.e., bones), has been suggested as a sustainable option to chemicals commonly used in cosmetic products, in particular to UV-filters in sunscreens. However, the environmental benefits and impacts of its production and use are still uncertain as they have never been quantified. In this paper, we report on toxicological characterization of CaP-N produced from incineration of fish meal in a pilot scale plant. Furthermore, we quantified the environmental burdens linked to the partial substitution of UV-filters by CaP-N through the life cycle assessment (LCA) comparing CaP-N with zinc oxide nanoparticles (ZnO NPs) as alternative option. CaP-N consists in a biphasic mixture 53:47 of hydroxyapatite:ß-tricalcium phosphate, and is made of round particles with a diameter in the range of a few microns. Toxicity tests on 4 aquatic species (Dunaliella tertiolecta, Tigriopus fulvus, Corophium insidiosum and Gammarus aequicauda) revealed that CaP-N does not produce any adverse effect, all the species showing EC/LC50 values higher than 100 mg L-1. Moreover, during the 96 h acute toxicity test on C. insidiosum, which is a tube-building species, the specimens built their tubes with the available CaP-N, further attesting the non-toxicity of the material. The LCA study showed that the environmental performance of CaP-N is better than that of ZnO NPs for 11 out of 16 impact categories analysed in this study, especially for the categories Ecotoxicity and Eutrophication of freshwaters (an order of magnitude lower), and with the exception of fossil resources for which CaP-N has a significantly higher impact than ZnO NPs (+140 %). Concluding, our study demonstrates that the replacement of ZnO NPs with CaP-N thermally extracted from fish bones in cosmetic products can increase their safety and sustainability.

Calcium Phosphate Particles Coated with Humic Substances: A Potential Plant Biostimulant from Circular Economy.

Nowadays, the use of biostimulants to reduce agrochemical input is a major trend in agriculture. In this work, we report on calcium phosphate particles (CaP) recovered from the circular economy, combined with natural humic substances (HSs), to produce a plant biostimulant. CaPs were obtained by the thermal treatment of Salmo salar bones and were subsequently functionalized with HSs by soaking in a HS water solution. The obtained materials were characterized, showing that the functionalization with HS did not sort any effect on the bulk physicochemical properties of CaP, with the exception of the surface charge that was found to get more negative. Finally, the effect of the materials on nutrient uptake and translocation in the early stages of development (up to 20 days) of two model species of interest for horticulture, Valerianella locusta and Diplotaxis tenuifolia, was assessed. Both species exhibited a similar tendency to accumulate Ca and P in hypogeal tissues, but showed different reactions to the treatments in terms of translocation to the leaves. CaP and CaP-HS treatments lead to an increase of P accumulation in the leaves of D. tenuifolia, while the treatment with HS was found to increase only the concentration of Ca in V. locusta leaves. A low biostimulating effect on both plants' growth was observed, and was mainly scribed to the low concentration of HS in the tested materials. In the end, the obtained material showed promising results in virtue of its potential to elicit phosphorous uptake and foliar translocation by plants.

Mussel Shell-Derived Macroporous 3D Scaffold: Characterization and Optimization Study of a Bioceramic from the Circular Economy.

Fish industry by-products constitute an interesting platform for the extraction and recovery of valuable compounds in a circular economy approach. Among them, mussel shells could provide a calcium-rich source for the synthesis of hydroxyapatite (HA) bioceramics. In this work, HA nanoparticles have been successfully synthesized starting from mussel shells (Mytilus edulis) with a two steps process based on thermal treatment to convert CaCO3 in CaO and subsequent wet precipitation with a phosphorus source. Several parameters were studied, such as the temperature and gaseous atmosphere of the thermal treatment as well as the use of two different phosphorus-containing reagents in the wet precipitation. Data have revealed that the characteristics of the powders can be tailored, changing the conditions of the process. In particular, the use of (NH4)2HPO4 as the phosphorus source led to HA nanoparticles with a high crystallinity degree, while smaller nanoparticles with a higher surface area were obtained when H3PO4 was employed. Further, a selected HA sample was synthesized at the pilot scale; then, it was employed to fabricate porous 3D scaffolds using the direct foaming method. A highly porous scaffold with open and interconnected porosity associated with good mechanical properties (i.e., porosity in the range 87-89%, pore size in the range 50-300 µm, and a compressive strength σ = 0.51 ± 0.14 MPa) suitable for bone replacement was achieved. These results suggest that mussel shell by-products are effectively usable for the development of compounds of high added value in the biomedical field.