Pigments—Lead-based whites, reds, yellows and oranges and their alteration phases

This review summarises the state-of-the-art of lead-based pigment studies, addressing their production, trade, use and possible alteration. Other issues, such as those related to the investigation and protection of artworks bearing lead-based pigments are also presented. The focus is mineralogical, as both raw materials and degradation products are mineral phases occurring in nature (except for very few cases). The minerals described are abellaite, anglesite, blixite, caledonite, challacolloite, cerussite, cotunnite, crocoite, galena, grootfonteinite, hydrocerussite, laurionite, leadhillite, litharge, macphersonite, massicot, mimetite, minium, palmierite, phosgenite, plattnerite, plumbonacrite, schulténite, scrutinyite, somersetite, susannite, vanadinite and an unnamed phase (PbMg(CO3)2). The pigments discussed are lead white, red lead, litharge, massicot, lead-tin yellow, lead-tin-antimony yellow, lead-chromate yellow and Naples yellow. An attempt is made to describe the history, technology and alteration of these pigments in the most complete manner possible, despite the topic's evident breadth. Finally, an insight into the analytical methods that can (and should) be used for accurate archaeometric investigations and a summary of key concepts conclude this review, along with a further list of references for use as a starting point for further research.

Increased urine chromium concentrations in a worker exposed to lead chromate due to medicinal herb intake

Background: Hexavalent chromium compounds are sensitizers of the skin and lung. Chronic exposure to hexavalent chromium compounds is associated with respiratory effects and ulceration and perforation of the nasal septum. Such compounds are also considered carcinogens of the lung and nasal and paranasal sinus. Objectives: To demonstrate the importance of studying occupational and non-occupational exposure when assessing the concentration of substances in the urine. Case study: A study was conducted of environmental chromium concentrations in the workplace. In addition, an occupational medical examination was performed, recording activities inside and outside the workplace, eating habits, blood lead and urine chromium at the beginning and end of the workday. Results: One worker exposed to lead chromate presented high chromium concentrations in urine (up to 62 µg/l before the working day and 52 µg/l at the end of the working day). Environmental chromium concentrations in the workplace were below 0.25 µg/m3. In view of the results, a full study was conducted of the patient’s habits outside work. He reported having bought a kilo of a medicinal herb infusion at a street market three weeks previously. The concentration of total chromium in the prepared infusion was 12000 µg/l. The patient stopped consuming the medicinal herb. Subsequently, the urine chromium analysis was below 0.5 µg/l. Discussion and Conclusions: This case is interesting because it demonstrates that the consumption of medicinal herbs can interfere with biological monitoring of workers exposed to hexavalent chromium compounds. This may give rise to confusion and can also create legal problems for companies and workers. It is important to provide advice to workers and to investigate their habits outside work, especially when there is a discrepancy between environmental and biological values. In this case, the increase in urinary chromium is due to the consumption of medicinal herbs.

Determining the authenticity of turmeric

The paper examines the problem of the composition instability in the ready ground spice, turmeric. Analysis of the prevalent methods for turmeric adulteration and substances used for these purposes is given. The visual assessment of color tints of the turmeric root, spices containing it and chemical dyes based on chromium salts is presented. The studies on determination of the lead and chromium content were carried out to study the content of these metals and test the hypothesis of using lead chromate as a dye in adulteration of turmeric. Using the method of electrothermal atomic absorption spectroscopy, it was found that the lead content in the analyzed turmeric samples varied from 1.72 ± 0.58 to 5.03 ± 1.80 mg/kg, while the chromium content was in a range of 5.56 ± 0.85 to 16.15 ± 2.32 mg/kg. As a result of species specific PCR, wheat DNA was revealed in all purchased samples of ground turmeric. The levels of the main raw material replacement were established, which were 0.14% to 14.95% with the correlation coefficient close to 100%; efficiency of the reaction was 1.95, which was 97.5% when expressed as percentage. These levels of an undeclared allergen in the product composition can cause a serious allergic reaction. The authors tested the hypothesis of introduction of sodium and potassium salts for correction of the color spectrum in the ready spice and its correspondence to the natural color within the color spectrum of turmeric. As a result of the complex study of the spice composition, quite high values of chromium were found, presumably not only from the lead chromate compound but also from chromic acid salts, as the high level of potassium that significantly exceeded the native content of this element was found.

Bismuth vanadate pigments

Bismuth vanadate pigments belong to the most important inorganic yellow pigments since their market introduction in the 1970s. They have substituted the greenish yellow lead chromate and cadmium sulfide pigments in a considerable number of applications. Bismuth vanadate pigments are based on bismuth vanadate with monoclinic or tetragonal structure. Their composition ranges from pure BiVO4 up to the mixed pigment 4BiVO4▪3Bi2MoO6, where molybdenum is incorporated in the structure. Bismuth vanadate pigments are characterized by excellent optical and application characteristics in particular regarding brightness of shade, hiding power, tinting strength, weather fastness, and chemical resistance.

Thermal Stability of Inorganic Pigments Synthesized from Galvanic Sludge

Pigments used in ceramic glazes have been obtained by chromium ions extraction from galvanic sludge and their precipitation as barium chromate and lead chromate from technological solutions. The chemical composition was determined by XRF method. Complex thermal analysis TG-DSC, XRD and SEM methods have been used for microstructural characterization and thermal treatment behaviour evaluation, in order to establish the compatibility with the ceramic matrix. XRD spectra have highlighted only lead chromate specific interferences in the monoclinic phase and barium chromate in the orthorhombic phase, suggesting an advanced degree of purity. Weight losses of 2.2% for barium chromate and 3.1% for lead chromate have been recorded on the TG curve at 800�C. As a result of thermal treatment, barium chromate has changed its colour from yellow to green.