Integrated methodologies in the study of pottery function

A fast testing procedure for the determination of VOCs in textile matrix using solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) was introduced. Samples were cut into small pieces and soaked in 5% methanol (v/v) saturated NaCl solution with supersonic pretreatment at 40±1°Cwater-bathing for 15 min and headspace exposure for 10 min at 50°C with stirring rate at 1100rmp. The influence of SPME adsorption time, stir speed, adsorption time and temperature, and gas chromatography (GC) inlet conditions for the SPME were investigated. Then the matrix solutions were extracted by headspace SPME and analysis by GC/MS. Under the optimized conditions, the limits of detection for target compounds were 0.005mg/kg with average recovery between 90.6-108.7%. The results obtained clearly showed the potential of SPME for efficient concentration of the target compounds and also demonstrated the reliability of this extraction technique for the monitoring of textile quality for the eco-marks.

A variety of pesticides have been used to control weeds, pests, and diseases to enhance crop yield. Pesticides applied in crops are often region-specific due to the differences in weather, production system, and agricultural policies. Pesticide residue in food crops not only affects the quality, but also threatens the health of consumers. Food contamination has become a universal concern, prompting various levels of regulation and monitoring. Generally, pesticide quantification is performed by gas chromatography (GC) combined with selective detectors, which helps to quantify one or more classes of pesticides at a time. Screening for a wide array of pesticides requires multiple runs utilizing different GC configurations. GC–mass spectrometry (MS) has been developed as a certified technique for identifying and quantifying various pesticides in a single run. Analysis of contaminants and harmful chemical residues in food got more importance as it results from the critical observation of consumers toward the advanced technologies of agricultural production and environmental pollution. A proper diet is commonly regarded as one of the key factors determining an individual’s health. Despite the nutritional benefit of fruits and vegetables, they may also contain substances that adversely affect human health. A considerable number of pesticides have a harmful effect already in low concentrations. In the analysis of pesticide residue, similarly to the analysis of other food contaminants, it is of great importance to develop multi-residue methods that enable monitoring complex multi-residue pesticides in a variety of samples. Recent studies on the estimation of pesticide residues in plant raw materials and ready food products indicate the universal incorporation of the liquid chromatography (LC)–MS technique in the analysis. Research data confirm that the highly sensitive LC–tandem mass spectrometry technique is characterized by selectivity and specificity and allows a high-throughput analytical process for confirming the quality of the result.

Recent Publications on Archaeological Ceramic Analyses and their Contributions to the Study of Ancient Pottery Technology

Gas chromatography/mass spectrometry (GC/MS) was applied to quantitative analysis of organic gunshot residues. A small particle of the residue was collected from an adhesive sheet laid on the floor in front of a barrel. Smokeless powder and its residues were dissolved in acetone and submitted to GC/MS. The ingredients of smokeless powder were quantified by mass chromatography. The peak area ratio of stabilizers to nitroglycerin (NG) in the residue showed almost same value in the original smokeless powder. These results will suggest that the residue analysis is useful for characterizing the original powder.

The site of Tell Atchana/Ancient Alalakh is located in the Amuq valley, now in the modern province of Hatay, in Southern Turkey. While it was previously thought that the site was abandoned towards the end of the Late Bronze Age, recent excavations at the site have demonstrated the presence of Iron Age levels, suggesting a prolonged period of occupation. This thesis presents a detailed analysis of the pottery assemblages excavated from the Iron Age levels of Alalakh; makes a major contribution to defining a new chronology for the site of Alalakh and sheds a new light on the last centuries of occupation. Based on the pottery assemblages this thesis proposes a new interpretation of the Early Iron Age period as being not a period of crisis and collapse but of accomplishment and regeneration. Moreover, by applying a more holistic and anthropological approach to the study of ceramics, this thesis investigates the patterns of consumption and of social dynamics in Early Iron Age Alalakh and links them within the broader regional framework of the Northern Levant. The morphological analysis carried out in this thesis defines a typology for the Iron Age pottery assemblages and establishes a relative chronology for the Iron Age levels. This enables the Iron Age settlement on Alalakh to be dated to the Iron Age I and II (12th-9th century BC). The functional analysis performed on the pottery assemblage recovered from square 42.10, the only square that yielded a reliable stratigraphy, results in the identification of the square as an open area devoted to the processing and consumption of food. This approach determines a change in the way food was cooked and displayed, but not in the way it was served and consumed. Finally this thesis draws conclusions related to continuity and change detectable in the local pottery assemblage and proposes a new historical narrative regarding Alalakh and the Amuq valley for the first centuries of the Early Iron Age.

This paper presents a thorough analysis of ornaments discovered in two Neolithic burials at Samborzec Site 1, providing valuable insights into their origins and significance. The artefacts, retrieved over six decades ago in the burials of a woman and child, have undergone extensive examination, including raw material identification, microwear studies, and the analysis of red residues found on their surfaces. While most of the ornaments concerned were crafted from marble, two beads were identified as Spondylus shells. Chemical analysis of residues, primarily found on the marble ornaments, revealed the presence of cinnabar, a red pigment of foreign origin. The remarkable similarities in ornaments between the investigated burials strongly suggest the association of both with LBK communities. The presented studies offer valuable insights into their object biographies, from the acquisition of raw materials from distant regions through their manufacture, assembly, and prolonged use as personal items. In this context, our research emphasizes their belonging to a shared Neolithic tradition in Europe.

Gunshot residue (GSR) is a complex chemical mixture that is created during the discharge of a firearm. Its detection and interpretation play a crucial role in the investigation of firearm incidents. Current GSR analysis is limited to inorganic GSR (IGSR), however, the evidential value could be strengthened by inclusion of organic GSR (OGSR). The present study aims to address this potential by proposing a categorisation system for relevant OGSR compounds and developing a methodology for the collection, extraction and analysis of both organic and inorganic GSR from a single sample. The organic composition of more than 50 propellant powders has been determined and compared against more than 200 propellant compositions reported in the literature. This work has resulted in a three-tier categorisation system for OGSR compounds, which together with the current IGSR classification will provide unequivocal identification of GSR materials with the possibility of discriminating between GSR from different ammunition types. Evaluation of MonoTrap extraction showed that this is an effective pre-concentration technique for the characterisation of propellants. Solid-phase microextraction (SPME), however, was the superior method for the extraction of OGSR compounds from various sampling media, including swabs and stubs. The optimised methodology involves GSR collection using carbon adhesive stubs followed by SPME gas chromatography – mass spectrometry (GC-MS) analysis of OGSR and subsequent scanning electron microscopy – energy-dispersive X-ray spectrometry (SEM-EDX) analysis for IGSR. This protocol has resulted in the detection of both characteristic IGSR and categorised organic compounds, demonstrating the ability to obtain a full chemical profile from a single sample. Detection of both first and second tier organic compounds provides complementary compositional information that could be used to discriminate between samples. Furthermore, this methodology requires no changes to the current sampling and IGSR analysis protocols and addresses the limited storage time of OGSR. Since GC-MS instruments are readily available in most analytical laboratories, implementation of the proposed protocol is feasible.

This paper presents a gas chromatography‐mass spectrometry (GC‐MS) organic residue analysis (ORA) of samples extracted from five Early Bronze Age ceramic bottles excavated at the archaeological site of Küllüoba in Anatolia (modern Turkey), and the first attempt at directly analysing the content of this category of products. Our results show that various types of liquid have been contained in different bottles and identify the presence of dicarboxylic and oleic acids with a large amount of palmitic acid in most samples, suggesting that they may have mostly contained a plant‐based oil. The presence of diterpenoids further shows the addition of ingredients such as conifer resin and other plant‐derived products. Overall, the analytical results presented here indicate the exchange of scented oils in Anatolia already during the late third millennium BCE. The different organic residue profiles contained in different samples also suggest a range of different recipes for these products.

Market economies are notoriously difficult to identify in the archeological record. This is particularly true in the subtropical Maya lowlands of Mexico, Guatemala, and Belize because most utilitarian items and consumables were made of highly perishable materials. We explore the hypothesis that ancient marketplaces can be identified through analysis of chemical residues in soils from open and easily accessible spaces in and about ancient Maya cities. We compared soil chemical signatures from a credible ancient marketplace location in the specialized trade center of Chunchucmil, Yucatan, Mexico to those from a modern marketplace at Antigua, Guatemala. We found extraordinarily high concentrations of phosphorus and zinc in the soil of Chunchucmil's proposed marketplace and the same high concentrations correlate well with food preparation and vegetable sales areas at the modern marketplace. These methods hold promise in resolving the vexing question of how large ancient Maya urban populations were sustained.

Molecular and isotopic analyses on prehistoric pottery from the Virués-Martínez cave (Granada, Spain)

Eight-month functional outcome from mania following a first psychiatric hospitalization

Despite the significant achievements of organic residues analysis of archaeological pottery, the sometimes low lipid recovery and the need to process increasingly large collections of sherds to tackle important archaeological questions require the development of a more efficient and rapid extraction method. In this paper we present a novel methodology for the extraction of absorbed organic residues directly from crushed archaeological ceramic using acidified methanol (H2SO4–MeOH 2% v/v, 70 °C, 1 h). This new protocol was tested by: (i) verifying the recovery of organic residues from previously studied archaeological vessels from different geographical regions, exhibiting a range of different lipid distributions often found in archaeological pottery, and (ii) demonstrating enhanced recovery of organic residues from potsherds that did not yield appreciable lipids when using the widely applied chloroform–methanol extraction. The application of the direct acidified methanol extraction recovers higher concentrations of lipid residues together with simultaneous production of methyl esters of fatty acids, allowing extraction and methylation to be completed in 20% of the time compared to conventional solvent extraction and derivatisation for gas chromatography (GC), gas chromatography mass spectrometry (GC-MS) and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS).

Rapid and effective sample clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography–mass spectrometry

Organic residue analyses of archaeological ceramics can provide important insights into ancient foodways. To date, however, there has been little critical reflection on how lipid residues might (or might not) reflect dietary practices or subsistence strategies more generally. A combination of ethnoarchaeological research and chemical and isotopic analyses of lipid residues from pottery made and used by modern Samburu pastoralists in northern Kenya was undertaken to supplement the interpretive framework used in archaeological investigations. A total of 63 potsherds were collected from various contexts, including settlement sites and rockshelters, and analysed using gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The results showed that the free fatty acids, palmitic (C16:0) and stearic (C18:0), dominated the lipid profiles, with extremely broad ranges of δ13C values. The majority of the Δ13C values from Samburu pots suggest that vessels were intensively used to process ruminant carcass products, yet the Samburu economy is not, in fact, meat-based at all. Despite an overall reliance on dairy products, milk is rarely processed in ceramic vessels, largely due to cultural prohibitions. Surprisingly, a number of vessels from one site, Naiborkeju Hill, were used to process dairy products. Compound-specific radiocarbon dating of lipids from these sherds suggests that this pottery originated from an earlier period, demonstrating a possible shift in ceramic use by pastoralist communities in this region over time. The overall conclusion is that lipid residues may not necessarily reflect, in a simple way, the day-to-day consumption or the perceived relative importance of different foodstuffs. In the Samburu case, lipid residues reflect the functional and ideological suitability of ceramics for processing only certain types of food (meat/fat/bones), despite an overall reliance on milk. These conclusions are important when considering the origins and development of African pastoralism, for example, as interpreted from the archaeological record.

The capacity of agricultural cultivation for carbon sequestration and emission reduction plays a key role in advancing the green and sustainable development of agriculture and achieving both emission reduction and carbon sink objectives. This study constructs an index for agricultural carbon sequestration and emission reduction capacity using spatial autocorrelation analysis, Theil index, and kernel density estimation, to thoroughly explore spatiotemporal changes and regional differences in carbon sequestration and emission reduction capacity across China and its different grain functional areas. Major findings include: (1) From 2000 to 2020, China’s agricultural carbon sequestration and emission reduction capacity exhibited a fluctuating upward trend, consistent in grain main production areas, while production–consumption and main marketing areas showed a fluctuating decline. (2) From 2000 to 2020, positive spatial correlation in carbon sequestration and emission reduction capacity increased at both national and regional levels, particularly in the main production and production–consumption areas, while the main consumption areas demonstrated a trend toward negative correlation. (3) The Theil index of China’s agricultural carbon sequestration and emission reduction capacity showed an overall fluctuating increase, with interregional differences contributing over 54%, significantly surpassing intra-regional contributions. Moreover, the main producing regions are the main source of the overall national variance. (4) Kernel density analysis highlights that there are significant differences in the distribution and evolution of carbon sequestration and emission reduction capacity among different grain functional areas, and the overall development is unbalanced. Therefore, each region needs to formulate tailored measures to improve agricultural carbon sequestration efficiency, promote regional sustainable development, and achieve carbon reduction goals.