Curly malachite on archaeological bronze: A systematic study of the shape and phenomenological approach of its formation mechanism

Curly malachite (CM) is found as a green cupric carbonate hydroxide corrosion product on archaeological bronze, mostly on artefacts retrieved from graves. In this paper, a morphological characterization approach is proposed, enabling the investigation of the formation process of CM. It is suggested that curly malachite precipitates from an aqueous solution, for which the surrounding soil conditions provide local triggers. Anthropic activities associated with ritual burials do not significantly affect the growth of CM. It is also confirmed that curly malachite is usually not a pseudomorph of formerly organic material. Although the understanding of the formation process is far from complete, this study has shown that CM is expected to be found more often than is currently recognized, due to its relatively simple formation mechanisms and boundary conditions.MSE-4MSE-

Testing non-destructive spectrometric methods for the identification and distinction of archaeological pine wood tar and birch bark tar

Archaeological findings prove the appearance and use of birch bark tar since the Middle Palaeolithic. The production and use of birch bark tar and pine wood tar has overlapped since at least the late Neolithic, but probably for much longer. The reliable chemical identification of such archaeological tar residues can offer valuable insights into, for example, ancient technical complexity, trade and culture. In this context, the scarcity of these mainly organic residue findings in the archaeological record bears the need for non-destructive analytical tools. However, there is currently no systematic proposed way for this purpose. We aim here to verify the organic nature and test the reliability of the identification of archaeological pine wood tar and birch bark tar with a combination of SEM-EDS, FTIR microspectroscopy in reflectance mode and XRD. We examined a set of experimental adhesive replicas of pine tar and birch tar in pristine form, but also after a three-year-long weathering experiment. Additionally, we studied a set of archaeological samples, consisting of Mesolithic bone/antler points with adhering hafting residues, form the Dutch North Sea. This research shows that degradation negatively influences the reliable verification and identification of the organic residue constituents significantly. SEM-EDS as a starting point of analysis verifies the residue's organic nature, but it cannot be used to identify birch or pine tar. XRD can identify crystalline additives in the adhesive mixture, like ochre and wax, as well as phases related to the artefact's environment of burial and provenance. Micro-FTIR is also capable of verifying the organic matter of the residue constituents. The differentiation of birch and pine tars is hindered by vibrational modes occurring in neighbouring wavenumbers for both tars, and by the limited research on degradation markers indicative of thermal treatment to prove tar production. Until reference collections also account for degradation and include a wide variety of adhesives, results of FTIR collected in reflectance mode are best treated with some caution.Team Joris DikTeam Amarante BottgerDelft Aerospace Structures and Materials LaboratoryGroup Alderlieste

A case study for scientific research prior to conservation of marine metal artefacts

A rare find of a high-status 17th century oval box, retrieved from a shipwreck, provided a unique opportunity to research the construction and finishing layers of an object that is untouched for 350 years. This case study was used to demonstrate the extent of data that can be gained from analytical techniques prior to conservation. The amalgam-gilt brass object was studied by optical and electron microscopy, X-radiography, micro-computed X-ray tomography, neutron tomography, X-ray fluorescence, X-ray diffraction, Rutherford backscattering spectrometry, proton-induced X-ray emission and gas chromatography. The results have led to a characterisation of the manufacturing methods used on the box and to a better understanding of the practicality of modern analytical methods and techniques in (maritime) archaeological research.RST/Neutron and Positron Methods in Material

Unravelling the construction of silver filigree spheres from a seventeenth century shipwreck using non-invasive imaging

The structure of five rare filigree spheres from a seventeenth century shipwreck was examined in order to unravel their condition, manufacturing process and function. This study focuses on the application of non-invasive imaging techniques: optical microscopy, X-radiography, X-ray micro-computed tomography and neutron computed tomography. A valuation of different aspects of the applied techniques was made, aiding stakeholders in decision-making on research and conservation. The combination of theory and scientific information was used to obtain an improved understanding of the manufacturing process and function of the filigree spheres.Geo-engineeringRST/Neutron and Positron Methods in Material

Change lost: Corrosion of Roman copper alloy coins in changing and variable burial environments

We studied the corrosion of Roman copper alloy coins that experienced alternations or progressive changes in their burial environment. We used coins that were still embedded in soil or in a concretion selectedfrom three professional excataved sites - Berlicum and Krommenie in the Netherlands and Kempraten in Switserland. mCT scanning and neutron scanning were used to record the 3-D properties of these coins prior to (destructive) analyses. It proved possible to tentatively identify the coins. Microscope observations and SEM-EDX analyses revealed complex corrosion processes, related to changing burial environments. In soil horizon with fluctuating groundwater levels in a region with upwelling reducing, iron-rich groundwater, the copper in a gunmetal coin is essentially replaced by iron oxides while tin remains and forms tin-oxide bands. Fluctuating redox conditions in marine-influenced environments was shown to transform a copper-alloy coin into strongly laminated copper sulphides with embedded gypsum crystals, with an outer surface of copper and copper-iron sulphides. Burial of bronze in a charcoal rich layer probably caused temporary highly alkaline soil conditions. This caused most of the copper to leach from this coin, leaving behind a laminated tin-dominated mass, with only a limited amount of (malachite) corrosion products remaining in the surrounding groundmass. In all three cases, corrosion processes tend to be anisotropic, probably because of cold-hammering of the coins during their manufacture. Such corrosion processes on massive copper alloy coins may produce features that may lead to their incorrect classification as subferrati, i.e. copper alloy coins with an iron core. Our results may help in future to distinguish strongly corroded massive coins from subferrati.RST/Neutron and Positron Methods in MaterialsGeo-engineerin