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In the majority of cases, the red color of cinnabar on objects of cultural heritage is well preserved, though turning black is often claimed and has been the subject of investigations. To evaluate conditions for the stability of the pigment and understand the reactions, in this paper the problem is approached from various viewpoints. First of all the natural form cinnabarite is compared with the artificially prepared pigment vermilion. This establishes a differentiation of types in terms of quality, depending on structural impurities. With regard to the pigment's reactions influencing the discoloration, the most commonly mentioned environmental factors, such as radiation or halogens, are evaluated. In relation to various usages, the pigment's structural stability is then viewed in connection with adjacent pigments, glues, and the substrate, which may lead to a brown or black coloration or even the release of mercury, whereas the color is preserved in most cases when used on lime or in ink and lacquer. Due to the materials' properties, attention is drawn to the fact that discoloration to a brownish-black is not necessarily a sign of damage and harmful reaction products, but may indicate good preservation of the painted material, provided that the mercury can be bound in the substrate.

Using gemstone microscope, infrared spectrometer, micro laser Raman spectrometer, and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) to test and analyze synthetic and natural cinnabar on the market. The results showed that when synthetic cinnabar was in block form, obvious needle like straight longitudinal stripes were visible, which had significant differences in morphology from natural cinnabar. The aggregation of natural cinnabar often contains white calcite associated minerals, which appear as white clumps or veins on the surface. The luster differs greatly from the diamond luster of the main cinnabar. At the same time, the Se element content of natural cinnabar is much higher than that of synthetic cinnabar, and the Se content can be used as a reference to distinguish the two.

This paper explores the chemistry of mercury as described in ancient alchemical literature. Alchemy’s focus on the knowledge and manipulation of natural substances is not so different from modern chemistry’s purposes. The great divide between the two is marked by the way of conceptualizing and recording their practices. Our interdisciplinary research group, composed of chemists and historians of science, has set off to explore the cold and hot extraction of mercury from cinnabar. The ancient written records have been perused in order to devise laboratory experiments that could shed light on the material reality behind the alchemical narratives and interpret textual details in a unique perspective. In this way, it became possible to translate the technical lore of ancient alchemy into the modern language of chemistry. Thanks to the replication of alchemical practices, chemistry can regain its centuries-long history that has fallen into oblivion.

Geochemical methods can identify the long-distance exchange of resources in the archaeological record. Cinnabar is a mineral with a limited number of geological sources; however, methods for determining the geological origin of cinnabar are constricted by the limited availability of comparative geological source materials. This study applies a multi-method approach to compare isotopic ratios of mercury and sulfur in archaeological specimens of cinnabar from museum collections and scientifically excavated materials from the Andes region of South America. We demonstrate that the δ 202 Hg to Δ 199 Hg relationship, assessed through Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS), falls along a predictive slope, while Isotope Ratio Mass Spectrometry (IR-MS) for sulfur (S) was not a reliable proxy for determining ore source. Furthermore, Hg isotope ratios from similar sites and contexts tended to cluster, suggesting that most sites exploited cinnabar from the same ore source. Statistical analyses support the idea that the Huancavelica deposit served as the primary source of cinnabar pigment for pre-Hispanic societies, while also revealing some intriguing divergences that suggest alternate sources were exploited during certain periods on the North and South Coasts of Peru. These results demonstrate that MC-ICP-MS analyses of mercury can be used to geochemically trace cinnabar ore in the Andes and beyond.

This article summarises the history of cinnabar, from its first uses in burials to modern oils on canvas. After a brief introduction on mercury and contamination issues, the article gets to the heart of the topic. First, mercury-based minerals significant for studying pigments, i.e . cinnabar, metacinnabar, hypercinnabar and calomel, are presented. Structural information and properties precede an overview of the geographic distribution of cinnabar deposits. The following section addresses the multiple uses of cinnabar, divided into funerary use, decorative use, lustre and Chinese lacquer production. The use of cinnabar for writing (ink), medicine and cosmetics is briefly described, and a shortlist of uncommon finds is further provided. The following section approaches inherent but less known topics such as cinnabar procurement, trade, production technology, application and alteration. An entire section is dedicated to calomel before concluding with an overview of the analytical methods for the characterisation and provenance investigation of cinnabar.

The cinnabar, a vivid red pigment, has been used by many ancient cultures around the world. Teotihuacan is one of the Mesoamerican capitals that used it. The physical characteristics of the mineral and its blood-red color gave it particularly high value and significance. A detailed study on the occurrence of the mineral in Teotihuacan revealed its particular use in funerary and ritual domains as well as in mural painting. On the one hand, this mineral can be considered as an indicator of social status, this resource—of prestige—being reserved for the elites and, on the other hand, its deposit on the body of the deceased was part of a ritual linked to the notion of rebirth. The discovery of cinnabar and mercury in the recently excavated tunnel under the temple of the Feathered Serpent, one of the most emblematic monuments of the city, confirms the symbolic importance of these two elements and their links with the cosmological thought of the ancient Mesoamerican cultures.

Today, mercury is a matter of concern for health and environmental authorities across western countries, and legislation has been passed and programs have been implemented for its total elimination from human activity. But this was not always the case: mercury and its compounds have been highly appreciated and used since remote times all over the world with very diverse purposes ranging from decorative, medicinal, metallurgical and symbolic. In particular, cinnabar (HgS, mercury sulfide), a mineral of an intense red color, has been considered in many cultures as an exotic raw material, highly valued and associated with the elites and sacred practice. In this paper, we examine one such case, set almost 5000 years ago, in Copper Age Iberia, by investigating mercury exposure through human bone. The study presented here includes a total of 170 samples from 70 different human individuals and 22 animals (plus one soil sample) from the Copper Age mega-site of Valencina, south-western Spain. It is the largest ever single-site study of exposure to mercury based on human bone in combination with cinnabar use. Abnormally high values are recorded in some individuals dating between 2900 and 2650 BC, especially in those buried in remarkable tombs belonging to the social elite of this period, but high levels of mercury are also recorded in the rest of the population. Three lines of interpretation are used to explain these results, including the manipulation of cinnabar (grinding it into powder, mixing it with other substances, using it for the decoration of objects, buildings and the human body), its direct consumption through ingestion or inhalation by a ‘special’ social group and the contribution of environmental factors. Based on the currently available evidence, which is carefully reviewed, Valencina represents the most intense and prolonged case of exposure to mercury recorded in human history, which makes it an important site to assess the long and complex history of use of this substance.

The stable isotope ratios of sulfur (δ34S relative to Vienna Cañon Diablo Troilite) in sulfates and sulfides determined by elemental analysis and isotope ratio mass spectrometry (EA/IRMS) have been proven to be a remarkable tool for studies of the (bio)geochemical sulfur cycles in modern and ancient environments. However, the use of EA/IRMS to measure δ34S in arsenides and sulfarsenides may not be straightforward. This difficulty can lead to potential health and environmental hazards in the workplace and analytical problems such as instrument contamination, memory effects, and a non-matrix-matched standardization of δ34S measurements with suitable reference materials. To overcome these practical and analytical challenges, we developed a procedure for sulfur isotope analysis of arsenides, which can also be safely used for EA/IRMS analysis of arsenic sulfides (i.e., realgar, orpiment, arsenopyrite, and arsenian pyrite), and mercury sulfides (cinnabar). The sulfur dioxide produced from off-line EA combustion was trapped in an aqueous barium chloride solution in a leak-free system and precipitated as barium sulfate after quantitative oxidation of hydrogen sulfite by hydrogen peroxide. The derived barium sulfate was analyzed by conventional EA/IRMS, which bracketed the δ34S values of the samples with three international sulfate reference materials. The protocol (BaSO4-EA/IRMS) was validated by analyses of reference materials and laboratory standards of sulfate and sulfides and achieved accuracy and precision comparable with those of direct EA/IRMS. The δ34S values determined by BaSO4-EA/IRMS in sulfides (arsenopyrite, arsenic, and mercury sulfides) samples from different origins were comparable to those obtained by EA/IRMS, and no sulfur isotope fractionations were introduced during sample preparation. We report the first sulfur isotope data of arsenides obtained by BaSO4-EA/IRMS.

The biomonitoring of atmospheric mercury (Hg) is an important topic in the recent scientific literature given the cost-benefit advantage of obtaining indirect measurements of gaseous Hg using biological tissues. Lichens, mosses, and trees are the most commonly used organisms, with many standardized methods for some of them used across European countries by scientists and pollution regulators. Most of the species used the uptake of gaseous Hg (plant leaves), or a mixture of gaseous and particulate Hg (mosses and lichens), but no method is capable of differentiating between main atmospheric Hg phases (particulate and gaseous), essential in a risk assessment. The purpose of this work was to evaluate different uptake patterns of biological tissues in terms of atmospheric Hg compounds. To accomplish this, the feasibility of two plant tissues from a tree commonly found in urban environments has been evaluated for the biomonitoring of gaseous Hg species in a Hg mining environment. Sampling included leaves and barks from Platanus hispanica and particulate matter from the atmosphere of the urban area around Almadén (south-central Spain), while analytical determinations included data for total Hg concentrations in biological and geological samples, Hg speciation data and total gaseous Hg (TGM). The results allowed us to identify the main Hg compounds in leaves and bark tissues and in atmospheric particulate matter, finding that leaves bioaccumulated only gaseous Hg (Hg[sup.0] and Hg[sup.2+]), preferably during daylight hours, whereas the barks accumulated a combination of TGM and particulate bound Hg (PBM) during the day and at night. Subsequent merging of the atmospheric Hg speciation data obtained from leaves and barks allowed indicative maps of the main sources of TGM and PBM emissions to be obtained, thereby perfectly delimiting the main TGM and PBM sources in the urban area around Almadén. This method complements TGM biomonitoring systems already tested with other urban trees, adding the detection of PBM emission sources and, therefore, biomonitoring all Hg species present in the atmosphere. Scenarios other than mining sites should be evaluated to determine the utility of this method for Hg biospeciation in the atmosphere.

The Gulf of Trieste (Northern Adriatic Sea, Italy) is the coastal area of the Mediterranean Sea most highly contaminated by mercury (Hg) due to fluvial inputs from the Isonzo/Soča River system, draining over 500 years’ worth of cinnabar extraction activity from the Idrija mining district (Western Slovenia). The aim of this research is to investigate the concentration of Hg in hair samples taken from the general population of the Friuli Venezia Giulia (FVG) Region coastal area, as a marker of chronic exposure to Hg. Three hundred and one individuals — 119 males and 182 females — were recruited by convenience sampling in Trieste in September 2021. An amount of approximately 100 mg of hair was collected from the occipital scalp of each participant to measure the respective Hg concentrations (expressed as mg/kg). Moreover, participants completed a self-report questionnaire collecting extensive socio-demographic and life-style information. A multiple linear regression analysis was employed to investigate factors associated with increased levels of Hg concentration in hair. A mean Hg concentration in hair of 1.63 mg/kg was found, slightly above the 1.0 mg/kg threshold recommended by the WHO for pregnant women and children, although still well below the no observed adverse effects level (NOAEL) of 10 mg/kg. Among respondents, 55.6% showed a Hg concentration in hair > 1 mg/kg, 22.9% > 2 mg/kg, and 2 participants exhibited Hg levels > 10 mg/kg. The adjusted mean hair Hg level increased in those subjects who reported a preference for shellfish/crayfish/mollusks (RC = 0.35; 95%CI: 0.16; 0.55), whereas it decreased in those who reported a preference for frozen fish (RC = -0.23; 95%CI: − 0.39; − 0.06). Though a risk alert for Hg exposure for coastal residents from FVG is deemed unnecessary at this time, it is recommended that pregnant women limit their ingestion of locally caught fish to < 4 servings/month.