New archaeomagnetic directions from Portugal and evolution of the geomagnetic field in Iberia from Late Bronze Age to Roman Times

This study presents new archaeomagnetic results from 33 combustion structures (kilns and hearths) from the archaeological sites of Castelinho, Crestelos, Olival Poço da Barca and Fonte do Milho in NE Portugal. The age of the investigated structures ranges from 1210 BC to 200 AD according to calibrated radiocarbon dating, thermoluminescence dating and archaeological constraints. Stepwise thermal and alternating field demagnetization isolate a single, stable, characteristic remanence component with very well defined directions. Rock magnetic analyses suggest low-Ti titanomagnetite/maghemite as the main magnetic carrier of the remanence. Mean directions are well grouped in most structures. The effect of thermoremanent anisotropy on mean directions has been evaluated and was found to be important. Inclination increases of between 2° and 13° after applying the anisotropy correction at specimen level. This highlights the requirement of evaluating this effect on the directions of small and flattened thin kilns and hearths. The 31 new directional data improve both the temporal and spatial distribution of the Iberian archaeomagnetic dataset from Late Bronze Age to Roman Times. Finally, a new directional palaeosecular variation curve for Iberia for the last twelve centuries BC is proposed. The curve has been computed using the bootstrap method and includes data coming from sites within 900 km of Madrid. The new palaeodirectional secular variation curve for Iberia is consistent with the Western European palaeosecular variation curve and with the prediction of regional European models

Epsilon iron oxide: Origin of the high coercivity stable low Curie temperature magnetic phase found in heated archeological materials

The identification of epsilon iron oxide (-Fe2O3) as the low Curie temperature high coercivity stable phase (HCSLT) carrying the remanence in heated archeological samples has been achieved in samples from two archeological sites that exhibited the clearest evidence of the presence of the HCSLT. This uncommon iron oxide has been detected by Confocal Raman Spectroscopy (CRS) and characterized by rock magnetic measurements. Large numbers of -Fe2O3 microaggregates (in CO) or isolated clusters (in HEL) could be recognized, distributed over the whole sample, and embedded within the ceramic matrix, along with hematite and pseudobrookite and with minor amounts of anatase, rutile, and maghemite. Curie temperature estimates of around 170 degrees C for CO and 190 degrees C for HEL are lower than for pure, synthetic -Fe2O3 (227 degrees C). This, together with structural differences between the Raman spectra of the archeologically derived and synthetic samples, is likely due to Ti substitution in the -Fe2O3 crystal lattice. The -Fe2O3--Fe2O3--Fe2O3 transformation series has been recognized in heated archeological samples, which may have implications in terms of their thermal history and in the factors that govern the formation of -Fe2O3

Electrochemical assessment of pigments-binding medium interactions in oil paint deterioration: a case study on indigo and Prussian blue

Abstract The degradation of laboratory oil paint film specimens containing indigo and Prussian blue pigments and pictorial samples from the Sant Francesc de Paula painting exhibited in the Tomàs Balvey Arxiu Museum (Cardedeu (Catalonia), Spain) has been studied by voltammetry of immobilized particles. This technique, combined with light microscopy, scanning electron microscopy-energy dispersive X-ray analysis, nanoindentation-atomic force microscopy, attenuated total reflectance-Fourier-transform infrared spectroscopy and gas chromatography–mass spectroscopy techniques permits the proposal of a dual scheme for the degradation of the pigments when naturally aged and submitted to accelerated UVA aging. Under conditions of moderate temperature, humidity and natural illumination, and low gradients of these parameters, Prussian blue acts as a radical scavenger moderating the production of reactive oxygen species produced in the oil binding medium by the action of ultraviolet radiation, resulting in the formation, in the solid state, of the solid-solution, {KFeIII[FeII(CN)6]} x {FeIII[FeIII(CN)6]}1–x , known as Berlin green, which then promotes the formation of indigo adducts with radicals. In several localized areas of the Sant Francesc de Paula paint showing strong degradation, Prussian blue acts as a promoter of the indigo oxidation to isatin, thus resulting in a considerable chromatic shift

First directional European palaeosecular variation curve for the Neolithic based on archaeomagnetic data

Neolithic, Chalcolithic and Bronze Age anthropogenic cave sediments from three caves from northern Spain have been palaeomagnetically investigated. 662 oriented specimens corresponding to 39 burning events (ash–carbonaceous couplets) from the three sites with an average of 16 samples per fire were collected. 26 new archaeomagnetic directions have been obtained for the time period ranging from 5500 to 2000 yr cal. BC. These results represent the oldest archaeomagnetic directions obtained from burnt archaeological materials throughout all Western Europe. Magnetisation is carried by pseudo-single domain low-coercivity ferromagnetic minerals (magnetite, magnetite with no significant isomorphous substitution and/or maghaemite). Rock-magnetic experiments indicate a thermoremanent origin of the magnetisation although a thermochemical magnetisation cannot be excluded. Combination of the new data presented here and the recent updated Bulgarian database allows us to propose the first European palaeosecular variation (PSV) curve for the Neolithic. A bootstrap method was applied for the curve construction using penalised cubic B-splines in time. The new palaeosecular variation curve is well constrained from 6000 BC to 3700 BC, the period with the highest density of data, showing a declination maximum around 4700 BC and a minimum in inclination at 4300 BC, which are not recorded by the recent global CALS10K.1b and regional SCHA.DIF.8K models due to the use of lake sediment data. Dating resolution by using the proposed PSV curve oscillates from approximately ±30 yr to ±200 yr for the period 6000 to 1000 yr BC, reaching similar resolution as radiocarbon dating. Considering the good preservation, age-control and widespread occurrence of burnt archaeological materials across Southern Europe, they represent a new source of data for geomagnetic field modelling, as well as for archaeomagnetic dating.Published124-1371A. Geomagnetismo e PaleomagnetismoJCR Journalrestricte

Electrochemical characterization of biodeterioration of paint films containing cadmium yellow pigment

[EN] The voltammetry of microparticles (VMP) methodology was used to characterize the biological attack of different bacteria and fungi to reconstructed egg tempera and egg linseed oil emulsion paint films containing cadmium yellow (CdS), which mimic historical painting techniques. When these paint films are in contact with aqueous acetate buffer, different cathodic signals are observed. As a result of the crossing of VMP data with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electrochemical microscopy (SECM), field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM), these voltammetric signals can be associated with the reduction of CdS and different complexes associated to the proteinaceous and fatty acid fractions of the binders. After biological attack with different fungi (Acremonium chrysogenum, Aspergillus niger, Mucor rouxii, Penicillium chrysogenum, and Trichoderma pseudokoningii) and bacteria (Arthrobacter oxydans, Bacillus amyloliquefaciens, and Streptomyces cellulofans), the observed electrochemical signals experience specific modifications depending on the binder and the biological agent, allowing for an electrochemical monitoring of biological attack.Financial support from the MINECO Projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P which are supported with ERDF funds is gratefully acknowledged. The authors also wish to thank Dr. José Luis Moya López, Mr. Manuel Planes Insausti, and Mrs. Alicia Nuez Inbernón (Microscopy Service of the Universitat Politècnica de València) for technical support.Ortiz-Miranda, A.; Domenech Carbo, A.; Domenech Carbo, MT.; Osete Cortina, L.; Valle-Algarra, FM.; Bolivar Galiano, F.; Martin Sanchez, I.... (2016). Electrochemical characterization of biodeterioration of paint films containing cadmium yellow pigment. Journal of Solid State Electrochemistry. 20(12):3287-3302. https://doi.org/10.1007/s10008-016-3349-6S328733022012Ratledge C (1994) Biochemistry of microbial degradation. Springer, BerlinCaneva G, Nugari MP, Salvadori O (2008) Plant biology for cultural heritage, the Getty Conservation Institute, Los AngelesSterflinger K (2010) Fungi: their role in deterioration of cultural heritage. Fungal Biol Rev 47–55 and references thereinGargani G (1968) Fungus contamination of Florence art masterpieces before and after the 1966 disaster. In: Walters AH, Elphick JJ (eds) Biodeterioration of materials. Elsevier, Amsterdam, pp. 252–257Seves AM, Sora S, Ciferr O (1996) The microbial colonization of oil paintings—a laboratory investigation. Int Biodeter Biodegr. 37:215–224Tiano P (2002) Biodegradation of cultural heritage: decay mechanisms and control methods. University of LisbonStrzelczyk AB (2004) Observations on aesthetic and structural changes induced in polish historic objects by microorganisms. Int Biodeter Biodegr. 53:151–156López-Miras M, Piñar G, Romero-Noguera J, Bolivar-Galiano FC, Ettenauer J, Sterflinger K, Martín-Sánchez I (2013) Microbial communities adhering to the obverse and reverse sides of an oil painting on canvas: identification and evaluation of their biodegradative potential. Aerobiologia 29:301–314Koszewski A, Rymuza Z, Reuther F (2008) Evaluation of nanomechanical, nanotribological and adhesive properties of ultrathin polymer resist film by AFM. Micro Engn 85:1189–1192Schabereiter-Gurtner C, Piñar G, Lubitz W, Rölleke S (2001) An advanced molecular strategy to identify bacterial communities on art objects. J Microbiol Meth 45:77–87Florian MLE (1996) The role of the conidia of fungi in fox spots. 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Rapid Intensity Decrease During the Second Half of the First Millennium BCE in Central Asia and Global Implications

Recent paleomagnetic studies have shown that important short-lived intensity fluctuations occurred during the first millennium BCE. However, the knowledge of the spatial and temporal extension of these features is still limited by the scarce availability of robust data. In this study we focus on the study of the intensity decrease that took place in Central Asia during the second half of the 1st millennium BCE after the high intensities that characterized the Levantine Iron Age Anomaly. Since previous archeointensities available for this period and region were obtained without accomplishing modern standards of quality, we present here new archeointensities that are derived from classical Thellier and Thellier experiments, including partial thermoremanent magnetization (pTRM) checks, thermoremanent magnetization (TRM) anisotropy and cooling rate corrections at the specimen level. The new 51 archeointensities, together with previous archeointensities, have been used to present a new local paleosecular variation curve for Central Asia. The results confirm the existence of an important geomagnetic field intensity decrease in South Uzbekistan from the 4th century BCE to the end of the 1st century BCE associated with rates of changes up to −15 μT/century. A critical analysis of the archeointensity global database indicates that this feature was present at continental scale, from Western Europe to Central Asia. However, this trend is not identified in other regions such as Japan or Mexico. Finally, the comparison with the dipole moment derived from recent global geomagnetic field reconstructions suggests a strong influence of non-dipolar sources upon this continental intensity feature.Financial support was given by the Spanish Ministry of Science and Innovation thorough the projects CERAC (HAR2016-75133-C3-1-P), CONCERAC (HAR2016-75133-C3-3-P), SPYKE (CGL2017-87015-P), SÚMATE (PID2020-113316GB-I00) and PULSES 5.K (PID2020-117105RB-I00). R. Bonilla-Alba thanks the FPI fellowship (PRE2018-085949) associated with the SPYKE project. This study has been also funded by the Ramón y Cajal program (contracts of M. Gómez-Paccard and V. Martínez-Ferreras, refs. RYC-2013-14405 and RYC-2014-15789). The authors wish to acknowledge the professional support of the CSIC Interdisciplinary Thematic Platform Open Heritage: Research and Society (PTI-PAIS). E. Beamud thanks the Geomodels Research Institute (UB) and the Grup de Geodinàmica i Anàlisi de Conques-2017SGR596 (Generalitat de Catalunya). A. Palencia-Ortas thanks the PTA contract of the Spanish Ministry of Science and Innovation

Estudio paleomagnético del dique de Messejana-Plasencia

A paleomagnetic investigation of 39 sites (591 samples) across the 530 km ot the Messejana-Plasenciadike has been carried out. Rock magnetic experiments indicate PSD low Ti titanomagnetite and magnetite as the minerals carrying the NRM. The samples where mostly demagnetised by thermal demagnetisation. Most sites exhibit a characteristic remanent component of normal polarity with the exception of two sites, where samples with reversed polarities have been observed. The paleomagnetic pole derived from the sites is well defined, with values ot Plat=70.5, Plong=238.0, K= 47.8 and ags=3.5. Paleomagnetic data indicates: (i) the dike had a brief emplacement time, (ii) the age of intrusion can be constrained between 180-200 Ma, (Hi) the high grouping of the VGPs directions suggest no important tectonic perturbations of the whole structure of the dike since its intrusion to the present

Rapid Intensity Decrease During the Second Half of the First Millennium BCE in Central Asia and Global Implications

Recent paleomagnetic studies have shown that important short-lived intensity fluctuations occurred during the first millennium BCE. However, the knowledge of the spatial and temporal extension of these features is still limited by the scarce availability of robust data. In this study we focus on the study of the intensity decrease that took place in Central Asia during the second half of the 1st millennium BCE after the high intensities that characterized the Levantine Iron Age Anomaly. Since previous archeointensities available for this period and region were obtained without accomplishing modern standards of quality, we present here new archeointensities that are derived from classical Thellier and Thellier experiments, including partial thermoremanent magnetization (pTRM) checks, thermoremanent magnetization (TRM) anisotropy and cooling rate corrections at the specimen level. The new 51 archeointensities, together with previous archeointensities, have been used to present a new local paleosecular variation curve for Central Asia. The results confirm the existence of an important geomagnetic field intensity decrease in South Uzbekistan from the 4th century BCE to the end of the 1st century BCE associated with rates of changes up to −15 μT/century. A critical analysis of the archeointensity global database indicates that this feature was present at continental scale, from Western Europe to Central Asia. However, this trend is not identified in other regions such as Japan or Mexico. Finally, the comparison with the dipole moment derived from recent global geomagnetic field reconstructions suggests a strong influence of non-dipolar sources upon this continental intensity feature