The identification of archaeological biomarkers is one of the main objectives of analytical chemistry in the archaeological field. However, no information is currently available on biomarkers able to unambiguously indicate the presence of olive oil, a cornerstone of Mediterranean ancient societies lifestyle, in an organic residue. This study aims to bridge this gap by a thorough characterization of the degradation products of extra-virgin olive oils (EVOOs) resulting from in-lab thermal oxidative treatments, with the primary goal of revealing potential archaeological biomarkers for olive oil. Thirty-three EVOOs sourced from eleven different monocultivars across five Italian regions (Sicily, Apulia, Lazio, Tuscany, and Liguria) and Spain, were analyzed before and after thermal oxidation. In addition, an identical thermal treatment was employed on pure triglyceride standards (triolein, trilinolein, and tristearin), due to the high concentration of their fatty acids in EVOO discerning their degradation patterns. A combination of analytical strategies was employed, including HPLC-MS and HPLC-ELSD for the complete evaluation of the intact lipids (triglycerides, diglycerides, and their oxidative species) in olive oils before and after oxidation, and HS-SPME-GC-MS and GC-FID for the characterization of secondary oxidation products formed by the thermal treatment. In addition, to elucidate the fatty acid distribution in the oxidized EVOOs by GC-MS and GC-FID techniques a derivatization step was performed to convert lipid compounds into trimethylsilyl (TMS) derivatives. A chemometric approach was used to thoroughly interpret the data obtained from intact and oxidized samples. This comprehensive investigation sheds light on the chemical transformations of EVOOs under thermal oxidative conditions and indicates mono-carboxylic acids such as pentanoic, hexanoic, heptanoic, octanoic, nonanoic, and decanoic acids as potential archaeological biomarkers for the presence of lipid substances coming from olive oil in archaeological organic residues. Finally, lipid contents from twenty-four real archaeological samples, grouped in amphorae (10), unguentaria (5), and lamps (9), excavated from the Roman domus of Villa San Pancrazio in Taormina (Italy), were determined. The analytical results obtained from amphorae samples revealed the presence of the selected olive oil-specific archaeological biomarkers, an information extremely interesting considering that this type of amphorae have so far been solely associated with the storage of wine.

In this article, the detailed description of a smartphone-based analytical method to turn a smartphone into a colorimeter is described and applied to mural painting replicas. The method consists of a camera characterization process, to estimate CIELAB values from RGB camera responses, correcting for potential experimental interferences, like the effect of the lighting/capture geometry or software for color modification and enhancement. Next, the estimated CIELAB descriptors were used to build a chemometric Support Vector Classifier to objectively distinguish among the colors of the different pigments. The method was validated in terms of color reproduction and classification performance.•A smartphone-based method is described to capture mural painting color.•A color gamut-specific camera characterization procedure is developed and the performance of the smartphone-based colorimeter is compared with a spectrophotometer.•A classification method based on the estimated CIELAB descriptors is validated in terms of classification performance.

This review explains the strategies behind genomics, proteomics, metabolomics, metallomics and isotopolomics approaches and their applicability to written artefacts. The respective sub-chapters give an insight into the analytical procedure and the conclusions drawn from such analyses. A distinction is made between information that can be obtained from the materials used in the respective manuscript and meta-information that cannot be obtained from the manuscript itself, but from residues of organisms such as bacteria or the authors and readers. In addition, various sampling techniques are discussed in particular, which pose a special challenge in manuscripts. The focus is on high-resolution, non-targeted strategies that can be used to extract the maximum amount of information about ancient objects. The combination of the various omics disciplines (panomics) especially offers potential added value in terms of the best possible interpretations of the data received. The information obtained can be used to understand the production of ancient artefacts, to gain impressions of former living conditions, to prove their authenticity, to assess whether there is a toxic hazard in handling the manuscripts, and to be able to determine appropriate measures for their conservation and restoration.

The optimization and application of a new hyphenated procedure for iron ionic speciation, i.e., high performance liquid chromatography (HPLC) with short cation-exchange column (50 mm × 4 mm) coupled to high resolution inductively coupled plasma optical emission spectrometry (ICP hrOES), is presented in this paper. Fe(III) and Fe(II) species were separated on the column with the mobile phase containing pyridine-2,6-dicarboxylic acid (PDCA). The total time of the analysis was approx. 5 min, with a significantly low eluent flow rate (0.5 mL min-1) compared to the literature. Additionally, a long cation-exchange column (250 mm × 4.0 mm) was used as reference. Depending on the total iron content in the sample, two plasma views were chosen, e.g., an attenuated axial (<2 g kg-1) and an attenuated radial. The standard addition method was performed for the method\'s accuracy studies, and the applicability was presented on three types of samples: sediments, soils, and archaeological pottery. This study introduces a fast, efficient, and green method for leachable iron speciation in both geological and pottery samples.

In the United States, the Native American Graves Protection and Repatriation Act (NAGPRA) provides a specific framework for the disposition of Native American Ancestral remains within its purview. However, samples such as a bone fragment, tooth, or other biological tissue taken from the remains of these Ancestors have been treated by institutions and researchers as independent of the individual from whom they were removed and used in destructive research such as paleogenomic and other archaeometric analyses without consultation, consent, and collaboration from Native American communities; are not cared for in keeping with the current best practices for Indigenous Ancestors; and are not likely to be repatriated to their communities. Here, we demonstrate that any biological samples removed from Ancestors who are covered under NAGPRA must also be handled according to the stipulations defined for \"human remains\" within the legislation. As such, we are not proposing a change to existing legislation, but rather best practices, specific to the context of the United States and NAGPRA, relating to the use of and care for biological samples taken from Native American Ancestors.

Although ceramic objects are an important part of the worldwide cultural heritage, few investigations on the effects of lithobiontic growth on their outdoor conservation are available in the literature. Many aspects of the interaction between lithobionts and stones are still unknown or strongly debated, as in the case of equilibria between biodeterioration and bioprotection. This paper describes research on the colonization by lithobionts on outdoor ceramic Roman dolia and contemporary sculptures of the International Museum of Ceramics, Faenza (Italy). Accordingly, the study i) characterized the mineralogical composition and petrographic structure of the artworks, ii) performed porosimetric measurements, iii) identified lichen and microbial diversity, iv) elucidated the interaction of the lithobionts with the substrates. Moreover, v) the measurements of variability in stone surface hardness and in water absorption of colonized and uncolonized areas were collected to assess damaging and/or protective effects by the lithobionts. The investigation showed how the biological colonization depends on physical properties of the substrates as well on climatic conditions of environments in which the ceramic artworks are located. The results indicated that lichens Protoparmeliopsis muralis and Lecanora campestris may have a bioprotective effect on ceramics with high total porosity and pores with very small diameters, as they poorly penetrate the substrate, do not negatively affect surface hardness and are able to reduce the amount of absorbed water limiting the water ingress. By contrast, Verrucaria nigrescens, here widely found in association with rock-dwelling fungi, deeply penetrate terracotta causing substrate disaggregation, with negative consequences on surface hardness and water absorption. Accordingly, a careful evaluation of the negative and positive effects of lichens must be carried out before deciding their removal. Regarding biofilms, their barrier efficacy is related to their thickness and composition. Even if thin, they can impact negatively on substrates enhancing the water absorption in comparison to uncolonized parts.

This study refers to the archaeometric analysis of ceramic fragments found in archaeological excavations around slave quarters of Colégio dos Jesuítas and São Bento plantations, both located in Campos dos Goytacazes - RJ. The question whether handmade ceramics were produced by the slaves themselves or acquired through local trade networks is an open and important question in the African diaspora. Samples of clay sources and the ceramic fragments, were analyzed using the EDXRF technique with the aid of multivariate statistical analysis.

A multimethod archaeometry study (zooarchaeological, isotopic, ancient DNA, paleobotanical, and radiocarbon dating) of a spider monkey sacrificed in the ceremonial center of Teotihuacan, Mexico (1 to 550 CE) is interpreted as a diplomatic gift exchange with neighboring Maya. Not only does this spider monkey provide the earliest known instance of primate translocation and captivity in Mesoamerica, it helps date incipient modes of interregional diplomacy between two major powers during Early Classic Mesoamerica: Teotihuacan and the Maya. Details of human-primate interaction include age at capture and transport (before ∼3 y of age), captive duration (over 2 y), anthropogenic diet (staple was maize, though secondary resources unique to anthropogenic diet including arrowroot and chili pepper were also found), context of sacrifice (tethered and associated with complete golden eagle and an array of other statecrafts), and general site context (including presence of Maya vessels and Maya-style murals). The timing of the spider monkey\'s sacrifice (250 to 300 CE) and its life history suggest a reconsideration of epigraphically attested militaristic involvement of Teotihuacan at certain Maya sites. We propose that a period of more multilateral and fluid ritual exchange with Maya dignitaries preceded the Teotihuacan state\'s eventual ascent to prominence.

In this study, 160 silver-copper alloy denarii and antoniniani from the 3rd century A.D. were studied to obtain their overall chemical composition. The approach used for their characterisation is based on a combination of physical, chemical, and chemometric techniques. The aim is to identify and quantify major and trace elements in Roman silver-copper coins in order to assess changes in composition and to confirm the devaluation of the currency. After a first cataloguing step, μ-EDXRF and SEM-EDX techniques were performed to identify the elements on the coins’ surface. A micro-destructive sampling method was employed on a representative sample of the coins to quantify the elements present in the bulk. The powder obtained from drilling 12 coins (keeping the two categories of coins separate) was dissolved in an acidic medium; heated and sonicated to facilitate dissolution; and then analysed by ICP-AES and ICP-MS. The two currencies had different average alloy percentages; in particular, the % difference of Ag was about 8%. The other elements were found in concentrations <1 wt%. Of these, the element highest in concentration were Pb and Sn, which is in agreement with the literature. The multivariate analysis performed on the data acquired revealed two groups of coins, corresponding to the two currencies.

Cacao seeds, Theobroma cacao, provide the basis for a ceremonially important Mesoamerican food. Past efforts to identify cacao in ceramics focused on highly decorative vessel forms associated with elite ceremonial contexts, creating assumptions as to how cacao was distributed and who could access it. This study examines 54 archaeological ceramic sherds from El Pilar (Belize/Guatemala) of Late Classic (600 to 900 CE) residential and civic contexts representing a cross-section of ancient Maya inhabitants. Identification of cacao in ancient sherds has depended on the general presence of theobromine; we used the discrete presence of theophylline, a unique key biomarker for cacao in the region. Analysis was done by grinding off all outside surfaces to reduce contamination, pulverizing the inner clay matrix, extracting absorbed molecules, and concentrating the extractions. In order to obtain especially high selectivity and low limits of detection, our study utilized the technique of resonance-enhanced multiphoton ionization coupled with laser-desorption jet-cooling mass spectrometry. This technique isolates molecules in the cold gas phase where they can be selectively ionized through a resonant two-photon process. Of the sherds analyzed, 30 samples (56%) were found to contain significant amounts of theophylline and thus test positive for cacao. Importantly, cacao is present in all contexts, common to all Maya residents near and far from centers.