Lithopone’s historical significance is further accentuated by the advancements and modifications that followed its inception. The 1874 patent by J.B. Orr, for instance, ushered in a new white pigment—Orr’s Zinc White. This innovation was attained by co-precipitating zinc sulfate and barium sulfide, followed by a calcination process. Further refinements marked the subsequent decades, the most notable being the enhancement of lightfastness achieved in the 1920s by introducing small amounts of cobalt salts before calcination.

Health advocates urge US regulators to ban common food coloring additive, by Tom Perkins, The Guardian, June 2, 2023

Titanium dioxide (TiO₂) is considered as an inert and safe material and has been used in many applications for decades. However, with the development of nanotechnologies TiO₂ nanoparticles, with numerous novel and useful properties, are increasingly manufactured and used. Therefore increased human and environmental exposure can be expected, which has put TiO₂ nanoparticles under toxicological scrutiny. Mechanistic toxicological studies show that TiO₂ nanoparticles predominantly cause adverse effects via induction of oxidative stress resulting in cell damage, genotoxicity, inflammation, immune response etc. The extent and type of damage strongly depends on physical and chemical characteristics of TiO₂ nanoparticles, which govern their bioavailability and reactivity. Based on the experimental evidence from animal inhalation studies TiO₂ nanoparticles are classified as “possible carcinogenic to humans” by the International Agency for Research on Cancer and as occupational carcinogen by the National Institute for Occupational Safety and Health. The studies on dermal exposure to TiO₂ nanoparticles, which is in humans substantial through the use of sunscreens, generally indicate negligible transdermal penetration; however data are needed on long-term exposure and potential adverse effects of photo-oxidation products. Although TiO₂ is permitted as an additive (E171) in food and pharmaceutical products we do not have reliable data on its absorption, distribution, excretion and toxicity on oral exposure. TiO₂ may also enter environment, and while it exerts low acute toxicity to aquatic organisms, upon long-term exposure it induces a range of sub-lethal effects.

As mentioned above, these oxide NPs are harmful in part because both anatase and rutile forms are semiconductors and produce ROS. Particularly, P25 kind has band-gap energies estimated of 3.2 and 3.0 eV, equivalent to radiation wavelengths of approximately 388 and 414 nm, respectively. Irradiation at these wavelengths or below produces a separation of charge, resulting in a hole in the valence band and a free electron in the conduction band, due to the electron movement from the valence to conduction bands. These hole–electron pairs generate ROS when they interact with H₂O or O₂ [43,44]. It was described that they can cause an increase in ROS levels after exposure to UV-visible light [45]. The NBT assay in the studied samples showed that bare P25TiO₂NPs produce a large amount of ROS, which is drastically reduced by functionalization with vitamin B2 (Fig. 5). This vitamin, also known as riboflavin, was discovered in 1872 as a yellow fluorescent pigment, [46] but its function as an essential vitamin for humans was established more than sixty years later, and its antioxidant capacity was not studied until the end of the XX century [47,48]. This antioxidant role in cells is partially explained because the glutathione reductase enzyme (GR) requires it for good functionality. This enzyme is the one in charge of the conversion of oxidized glutathione to its reduced form which acts as a powerful inner antioxidant and can quench the ROS [49,50]. The cost of this action is that the glutathione is converted to the oxidized form and needs to be recovered by the GR. Consequently, the cells need more vitamin B2. Another glutathione action is the protection against hydroperoxide. This activity is also mediated by riboflavin. Therefore, local delivery of this vitamin seems to significantly help the cells in their fight to keep the oxidative balance, once they are exposed to high levels of ROS.

Nano-sized P25TiO₂NPs were kindly donated by Dr. Scaiano, Ottawa University (Canada). Riboflavin (vitamin B2) was from Sigma and ascorbic acid (vitamin C) and KBr (for IR pills) were from Cicarelli. Base cream for the animal experiments was purchased from Todo Droga and the LED panel was built ad hoc.

Having thus described the origin and uses of the pigment, we now come to the question, what is lithopone? It is, in short, a chemical compound usually consisting of 30.5 per cent zinc sulphide, 1.5 per cent zinc oxide and 68 per cent barium sulphate, but these proportions vary slightly in the different makes. Lithopone of this composition is sold as the highest grade, either as red seal or green seal, as it best suits the idea of the manufacturer. Many manufacturers, especially in Europe, sell and also export other brands under other seals, containing 24, 20, 18 and as little as 12 per cent of zinc sulphide with very small percentages of zinc oxide, the balance being usually barium sulphate, but sometimes certain portions of China clay or gypsum (calcium sulphate) or whiting (calcium carbonate). Such brands are not a chemical compound, but mechanical mixtures of the chemically compounded lithopone and the admixtures referred to.

2: Clarification mechanism of coagulant

Chemical coagulation is a process in which chemical agents (coagulants) are added to water treatment to make colloidal dispersion system destabilize and agglomerate. In the coagulation process, small suspended particles and colloidal impurities are aggregated into larger solid particles to separate particulate impurities from water, which is called coagulation clarification.

After adding coagulant into water, colloidal particles and other small particles can be polymerized into larger flocs through the comprehensive action of mixing, coagulation and flocculation. The whole process of coagulation and flocculation is called coagulation.

(1) Destabilization and condensation of colloids

Adding electrolyte to water can compress the electric double layer and destabilize the colloid. The main mechanism is that the electric double layer of colloidal particles in water is compressed or neutralized by adding aluminum salt or iron salt coagulant. The coagulant and raw water are mixed rapidly and evenly, and a series of chemical reactions are produced to destabilize. This process takes a short time, generally about 1 min. Some cationic polymers can also play a role in the destabilization and condensation of colloids in water. These polymers have a long chain structure and positive charge in water. Their destabilization and condensation of colloids in water is due to the interaction of van der Waals force adsorption and electrostatic attraction.

(2) Flocculation and formation of floc (alum)

The particle size of the initial flocculate formed by colloid destabilization and coagulation in water is generally more than 1 m. at this time, Brownian motion can no longer push them to collide and form larger particles. In order to make the initial flocs collide with each other to form large flocs, it is necessary to input additional energy into the water to produce a velocity gradient. Sometimes it is necessary to add organic polymer flocculant into water, and the adsorption bridging effect of long chain molecules of flocculant is used to improve the probability of collision and adhesion. Flocculation efficiency usually increases with the increase of flocculate concentration and flocculation time.

Compared with polyaluminum chloride, polyaluminum chloride has the advantages of high density, fast settling speed and wide pH adaptability; the coagulation effect is less affected by temperature than that of polyaluminum sulfate; however, when adding ferric salt, it should be noted that when the equipment is not in normal operation, the iron ions will make the effluent color, and may pollute the subsequent desalination equipment.