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THE OBSCURE HISTORY OF A UBIQUITOUS PIGMENT: PHOSPHORESCENT LITHOPONE AND ITS APPEARANCE ON DRAWINGS BY JOHN LA FARGE

This article discusses the discovery of phosphorescent lithopone on watercolor drawings by American artist John La Farge dated between 1890 and 1905 and the history of lithopone in the pigment industry in the late 19th and early 20th centuries. Despite having many desirable qualities for use in white watercolor or oil paints, the development of lithopone as an artists' pigment was hampered by its tendency to darken in sunlight. Its availability to, and adoption by, artists remain unclear, as colormen's trade catalogs were generally not explicit in describing white pigments as containing lithopone. Further, lithopone may be mistaken for lead white during visual examination and its short-lived phosphorescence can be easily missed by the uninformed observer. Phosphorescent lithopone has been documented on only one other work-to-date: a watercolor by Van Gogh. In addition to the history of lithopone's manufacture, the article details the mechanism for its phosphorescence and its identification aided by Raman spectroscopy and spectrofluorimetry.

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1. Using roasting and leaching method. The reaction equation is as follows:

For research published in 2022 study in the journal Food and Chemical Toxicology, scientists examined “the genotoxicity and the intracellular reactive oxygen species induction by physiologically relevant concentrations of three different TiO2 nanomaterials in Caco-2 and HT29-MTX-E12 intestinal cells, while considering the potential influence of the digestion process in the NMs’ physiochemical characteristics.” They found a “DNA-damaging effect dependent on the nanomaterial,” along with the micronucleus assay suggesting “effects on chromosomal integrity, an indicator of cancer risk, in the HT29-MTX-E12 cells, for all the tested TiO2 nanomaterials.” Researchers concluded that the results showcase “evidence of concern” regarding titanium dioxide used as a food additive.

Titanium dioxide is considered safe for use in cosmetics products by expert bodies around the world, including Europe's Scientific Committee on Consumer Safety (SCCS) and the U.S. Food and Drug Administration (FDA). Nano grade titanium dioxide has been assessed by the SCCS and is approved by the European Commission for use as a UV filter.

But this is just the tip of the ice berg so many articles & studies are coming out challenging the safety of Titanium Dioxide in our food supply & personal care products.

The skin of an adult person is, in most places, covered with a relatively thick (∼10 μm) barrier of keratinised dead cells. One of the main questions is still whether TiO₂ NPs are able to penetrate into the deeper layers of the skin. The majority of studies suggest that TiO₂ NPs, neither uncoated nor coated (SiO₂, Al₂O₃ and SiO₂/Al₂O₃) of different crystalline structures, penetrate normal animal or human skin. However, in most of these studies the exposures were short term (up to 48 h); only few long-term or repeated exposure studies have been published. Wu et al.83 have shown that dermal application of nano-TiO₂ of different crystal structures and sizes (4–90 nm) to pig ears for 30 days did not result in penetration of NPs beyond deep epidermis. On the other hand, in the same study the authors reported dermal penetration of TiO₂ NPs with subsequent appearance of lesions in multiple organs in hairless mice, that were dermal exposed to nano-TiO₂ for 60 days. However, the relevance of this study for human exposure is not conclusive because hairless mice skin has abnormal hair follicles, and mice stratum corneum has higher lipid content than human stratum corneum, which may contribute to different penetration. Recently Sadrieh et al. performed a 4 week dermal exposure to three different TiO₂ particles (uncoated submicron-sized, uncoated nano-sized and coated nano-sized) in 5 % sunscreen formulation with minipigs. They found elevated titanium levels in epidermis, dermis and in inguinal lymph nodes, but not in precapsular and submandibular lymph nodes and in liver. With the energy dispersive X-ray spectrometry and transmission electron microscopy (TEM) analysis the authors confirmed presence of few TiO₂ particles in dermis and calculated that uncoated nano-sized TiO₂ particles observed in dermis represented only 0.00008 % of the total applied amount of TiO₂ particles. Based on the same assumptions used by the authors in their calculations it can be calculated that the total number of particles applied was 1.8 × 10¹³ /cm² and of these 1.4 x10⁷/cm² penetrated. The surface area of skin in humans is around 1.8 m²  and for sun protection the cream is applied over whole body, which would mean that 4 week usage of such cream with 5 % TiO₂ would result in penetration of totally 2.6 × 10¹⁰ particles. Although Sadrieh et al.concluded that there was no significant penetration of TiO₂ NPs through intact normal epidermis, the results are not completely confirmative.

The major restraint to the global Lithopone market is the availability of numerous white pigment substitutes. It can be replaced by other inorganic white pigments such as Titanium Dioxide (TiO2) and Sachtolith. Among these substitutes, the introduction of TiO2 has reduced the commercial importance of Lithopone white pigment. Compared to other white pigments, TiO2 has high brightness and refractive index, which results in lower pigment loading. 

Food containing titanium dioxide that is lawfully placed on the EU market before 7 August 2022 may remain on the market until its date of minimum durability or its ‘use-by’ date has passed. Food produced or placed on the market after 7 August 2022 cannot contain titanium dioxide. The ban on the use of titanium dioxide is effective in each EU Member State, and in Northern Ireland. Some third countries, such as the United Kingdom (excluding Northern Ireland), continue to permit the use of titanium dioxide.