Surface yellowing and fragmentation as warning signs of depolymerisation in Baltic amber

It is well known that the surrounding environment affects the initiation and rate of degradation of Baltic amber, causing changes in visual and mechanical properties. However, the mechanisms by which oxygen, the most important agent of degradation, causes those alterations are still unknown. Knowledge of such mechanisms would allow developing more efficient preventive conservation measures for amber artefacts in museums than those available today. In this study, an experiment using accelerated thermal ageing was conducted on representative Baltic amber samples. Changes in colour, topography and chemical properties were assessed regularly using non-destructive techniques, to identify the degradation phenomena which play a significant role during the discolouration and fragmentation processes of amber surfaces. The breakdown of the amber polymer chains, caused by oxidative radical reactions, was determined by means of FT-Raman spectroscopy and involved the formation of olefinic bonds in the terminal position. This depolymerisation process was correlated to modifications in colour, particularly yellowing, and in topographic features, analysed by spectrocolorimetry and confocal profilometry respectively. Thus, surface yellowing and fragmentation of amber objects in museum collections may act together as indicators of progressive depolymerisation.     

Applications of diamond crystal ATR FTIR spectroscopy to the characterization of ambers

Diamond crystal ATR FTIR spectroscopy is a rapid technique with virtually no sample preparation which requires small sample amounts and showed potential in the study of ambers. FTIR spectra of ambers present discriminating patterns and can be used to distinguish amber from immature resins as copal, to determine local or Baltic origin of archaeological ambers and to detect most of the falsifications encountered in the amber commercialisation.     

Analytical methods to differentiate Romanian amber and Baltic amber for archaeological applications

The study aims to establish several definite criteria which will differentiate Romanian amber and Baltic amber to certify the local or Baltic origin of the materials found in archaeological sites on the Romanian territory, by using light microscopy and performing analytical methods, such as Fourier transform infrared spectroscopy-variable angle reflectance and liquid chromatography with mass spectrometry detection. Experiments especially by Fourier transformed infrared spectroscopy, were applied to a wide range of samples with controlled origin. The methods were optimised and resulted in premises to apply the techniques to analysis of the archaeological material.      

Raman spectroscopic study on archaeological glasses in Thailand: ancient Thai glass

Glasses have been used as ornamental and decorative objects in Thailand for several hundred years as seen in archaeological artifacts, such as glass beads found throughout the regions. Decorative glasses can generally be seen as architectural components in Buddhist temples and old-styled palaces. They came in various colors ranging from transparent to amber, blue, green and red of different shades and tones. Fragments of archaeological glass samples were characterized for the first time using Raman spectrophotometer with the aim of obtaining information that would lead to the identification of the glass samples by means of laser scattering. The samples were also investigated using other techniques, such as proton induced X-ray emission spectroscopy, scanning electron microscopy cooperated with energy dispersive X-ray fluorescence spectrometer and synchrotron radiation to induced X-ray fluorescence. The results showed that they were mostly lead-silica based glasses whose colors were induced by metal ions. The differences in chemical compositions were confirmed by Raman signature spectra.     

Use of EIS for the evaluation of the protective properties of coatings for metallic cultural heritage: a review

The best way to reduce the degradation of metallic cultural heritage is through preventive conservation measures but, in many cases, it is not possible to obtain adequate environmental conditions, and it is necessary to apply coatings to the artefacts in order to protect them against corrosion. There is a continuous search in the metal conservation community for new and improved coatings that provide a better protection to the objects whilst respecting the special requirements of the conservation–restoration ethics. Whilst electrochemical techniques have a long tradition in conservation–restoration treatments for metallic cultural heritage, the evaluation of protective coatings using electrochemical impedance spectroscopy (EIS) has only been used very recently. EIS is a very well-established method to investigate metal coatings for general purposes and has many advantages that make it especially suitable for testing coatings for metallic works of art. This paper makes a review of the use of EIS for testing coatings for metallic cultural heritage from the first publications in the mid-1990s to the last papers. The experimental setup used, the types of coatings and metals investigated and the interpretation of the results are reviewed and compared with the use of EIS for testing general purpose anti-corrosive coatings.     

Preliminary thermal characterization of natural resins from different botanical sources and geological environments

The preliminary studies on thermal behavior of differently aged natural resins from Russia (Khatanga), Dominican Republic (El Valle), Colombia and Poland (Jantar) were performed. Thermal stability and behavior under elevated temperature were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC), while the differences in the structure and composition by FT-IR spectroscopy. Analyzed resins show different thermal effects during heating suggesting that possible post-reactions and structural changes occurred. TG results indicated that Dominican, Russian and Colombian resins present relatively high thermal stability under air conditions in the range of 228–300 °C, whereas the mass loss of 5mass% at about 217 °C was observed for Baltic amber. During DSC experiments, the analyzed resins expose thermal events which make impossible determination of glass transition temperature in a raw sample. The results indicate that both TG and DSC cannot be considered as methods for age dating of natural resins and more advanced techniques should be applied. Careful analysis of FT-IR data in the carbonyl region may provide additional information about the composition and history of the natural resin.

     

Aromatic compounds in molecular phase of Baltic amber-synchronous luminescence analysis

Synchronous luminescence analysis was performed in order to identify aromatic compounds in solvent extracts of Baltic amber. The investigated extracts were obtained, for comparisons, as products of extraction by various techniques and solvents. Methylene chloride and ethanol were applied independently for extraction at the ambient temperature (conservative extraction), as well as at the temperature of solvent boiling (extraction in Soxhlet apparatus). Ethanol, as the solvent, was also used for extraction in an ultrasonic bath and for the decoction process. The extraction, by techniques mentioned, of the analysed amber has resulted in products generally containing the same groups of aromatics: mainly naphthalenes, phenanthrenes and anthracenes. Among phenanthrenes, in all samples the retene was also identified, being one of the characteristic links of the diagenetic chain of chemical transformations of vegetal precursors. The identification of a series of individual compounds made, using the synchronous luminescence technique, was verified by the record of conventional emission and excitation spectra. Presented identified compounds were also confirmed by the results of GC-MS analysis. The luminescence analysis was also performed comparatively for fossil resin from Galicia, Spain (Cretaceous) older than Baltic amber (Tertiary, Eocene). The obtained preliminary results of synchronous luminescence analysis suggest the possibility of diversification in this manner of fossil resins of various ages by characterisation of aromatisation degree and alkyl substitution of aromatic rings. It is since well known that aromatisation progress is an indicator of a natural process of maturation of fossil organic matter. However, a greater number of samples should be taken to further testify to the investigations.     

Inhibiting the Inevitable; Current Approaches to Slowing the Deterioration of Plastics

Once plastics objects are registered in museum collections, the institution becomes responsible for their long term preservation, until the end of their useful lifetime. Plastics appear to deteriorate faster than other materials in museum collections and have a useful lifetime between 5 and 25 years. Preventive or inhibitive conservation involves controlling the environments in which objects are placed during storage and display, with the aim of slowing the major deterioration reactions. Once in progress, degradation of plastics cannot be stopped or reversed, so the aim of preventive conservation is to ‘buy time’ for the object. Inhibitive conservation of plastics involves the removal or reduction of factors causing or accelerating degradation including light, oxygen, acids, relative humidity and acidic breakdown products. Specific approaches to conservation have been developed for cellulose nitrate, cellulose acetate, PVC and polyurethanes by considering the most effective action to inhibit their major degradation pathways. The purpose of this article is to outline the main factors causing degradation of the least stable plastics in museum collections and present an overview of the conservation treatments established to date. Recent research has suggested that some of the conservation practices to slow the rate of deterioration in use today, particularly those for cellulose nitrate and acetate, are poorly effective and that alternatives should be evaluated. One alternative is low temperature storage.     

Thermal desorption/gas chromatography/mass spectrometry approach for characterization of the volatile fraction from amber specimens: A possibility of tracking geological origins

Research on the chemical composition of fossil resins has evolved during the last decades as a multidisciplinary field and is strongly oriented toward the correlation with their geological and botanical origin. Various extraction procedures and chromatographic techniques have been used together for identifying the volatile compounds contained in the fossil resin matrix. Hyphenation between thermal desorption (TD), gas chromatography (GC) and mass spectrometry detection (MS) has been chosen to investigate the volatile compounds fraction from ambers with a focus on Romanite (Romanian amber) and Baltic amber species. A data analysis procedure was developed for the main purpose of fingerprinting ambers based on the MS identity of the peaks generated by the volatile fraction, together with their relative percentual area within the chromatogram. Chromatographic data analysis was based entirely on Automated Mass Spectral Deconvolution & Identification System (AMDIS) software to produce deconvoluted mass spectra which were used to build-up a mixed mass spectra and relative retention scale library. Multivariate data analysis was further applied on AMDIS results with successful discrimination between Romanite and Baltic ambers. A special trial was conducted to generate pyrolysis “like” macromolecular structure breakdown to volatile compounds by gamma irradiation with a high absorbed dose of 500 kGy. Contrary to our expectations the volatile fraction fingerprints were not modified after irradiation experiments. A complementary non-destructive new approach by ESR spectroscopy was also proposed for discriminating between Romanite and Baltic ambers.     

Raman microspectroscopic studies of amber resins with insect inclusions

Raman microscope spectra of specimens of Baltic and Mexican amber resins containing insect inclusions have been analysed using near-infrared excitation to assess the potential for discrimination between the keratotic remains of the insects and the terpenoid matrix. For the Mexican amber specimen the insect spectra exhibit evidence of significant protein degradation compared with the insect remains in the Baltic amber specimen. In both cases the Raman spectra of the insect remains are still distinguishable from the amber resins. Despite its better preservation, however, no spectra could be obtained from the inside of the larger insect preserved in the Baltic amber in agreement with the observation that most insect inclusions in amber are hollow. It is noted that the Mexican amber insect is located adjacent to a large gas bubble in the amber matrix, to which the observed degradation of the insect and its poor state of preservation are attributed. It is concluded that Raman spectra of insect inclusions can provide useful information about the chemical composition of the remains and that confocal microscopy is particularly advantageous in this respect.     

Spectroscopic investigation of a ‘Virgin of Sorrows’ canvas painting: A multi-method approach

The investigation of unmatched ancient objects is an attentive and arduous activity to conservation scientists. An important aspect of art analysis is the question on sampling and avoiding damage on the artefact during the study. A possible way to maximize the information that is extracted from the historical object is using several sensitive micro-analytical techniques on the same micro samples. As an illustration of this multi-method approach, in this work, a canvas painting ‘Virgin of Sorrows’ was studied and its materials were analysed in order to roughly date and to authenticate this object of art. Proton induced X-ray emission (PIXE), neutron activation analysis (NAA), optical microscopy, scanning electron microscopy (SEM), micro-Raman spectroscopy (MRS) and Fourier transform infrared spectroscopy (FT-IR) were used, obtaining successful results. These methods allowed identifying the different inorganic pigments (iron oxide, carbon black, white lead, Prussian blue) as well as indigo. Optical microscopy and SEM revealed the layered structure of the samples, while FT-IR enabled to determine the nature of the varnish used (shellac). By using these complementary techniques, it was possible to identify the materials in the painting, which are indicative for the period of manufacturing the artwork.     

Identification of volatile degradation products from Baltic amber by headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry

The aim of this study was to test and develop techniques for the detection and identification of volatile compounds released as degradation products by Baltic amber. During a preliminary investigation, the off-gassing of acidic volatiles was detected through the corrosion of lead coupons. The corrosive compounds released by the material were then identified as formic acid and acetic acid by headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry. During an advanced investigation, based on the use of artificial ageing to initiate degradation of model amber samples in different microclimates, the detected formic acid and acetic acid off-gassing appeared to be more intense in a dry environment with normal oxygen concentration. The release of formic and acetic acids by the amber was likely the result of radical reactions which should be investigated in further studies.     

Mass spectrometry in the characterization of ambers. II. Free succinic acid in fossil resins of different origin

Baltic amber contains high levels of succinic acid, most of which is part of the polymer framework, and only recently has the presence of microcrystals of free succinic acid been documented by scanning electron microscopy and X‐ray diffraction analysis. The determination of succinic acid can be used for an easy identification of Baltic amber among other fossil resins and to distinguish it from imitations, widely diffused on the market, produced with natural or modified recent or sub‐fossil resins, such as copals. We report here a simple method, based on negative ion electrospray ionization mass spectrometry, for evaluating the free succinic acid content in water/methanol extracts of ambers from different origin, using a sample of about 20 mg. The limit of quantification is better than 1 ppm and, when applied to a set of amber samples of different origin, it was able to distinguish those of Baltic origin (showing free succinic acid levels in the range 50–400 ppm) from the others (for which succinic acid was undetectable, i.e. at levels lower than 1 ppm). Copyright © 2009 John Wiley & Sons, Ltd.     

Total reflection X-ray fluorescence and archaeometry: Application in the Argentinean cultural heritage

Archaeometry is an interdisciplinary research area involved in the development and use of scientific methods in order to answer questions concerned with the human history. In this way the knowledge of archaeological objects through advanced chemical and physical analyses permits a better preservation and conservation of the cultural heritage and also reveals materials and technologies used in the past. In this sense, analytical techniques play an important role in order to provide chemical information about cultural objects. Considering the non destructive characteristic of this study, analytical techniques must be adequate in order to prevent any alteration or damage and in addition to allow the conservation of their integrity. Taking into account the irreplaceable character of the archaeological and artistic materials considered in this study, analytical techniques must be adequate in order to prevent any alteration or damage and in addition to allow the conservation of their integrity.     

Formaldehyde activity on historical glass objects in museum microclimate

Degradation of some cultural heritage monuments has been caused by interaction with the closest environment (micro-climate). Amount of separate compounds is very small and because of it, this fact becomes neglected. Time and temperature can induce their activity finally causing deterioration. In this category organic compounds can be interpreted as one of museum show - case element. This statement has been improved by testing glass objects and their suitable sensors (model glasses). Destructive activity of formaldehyde on historical glasses belonging to the XVIII-th c. objects with totally different compositions has been confirmed by carried out experiments. For historical material which is very limited, sensor glass method has been applied. Sensors are prepared on the base of results of chemical analyses of original glass chemical analyses and melted on laboratory scale (according to historical data). Induced corrosion for sensor supports knowledge about deterioration process in real micro-environmental conditions. The following testing methods were used: scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), optical interferometer (OI), inductively couple plasma (ICP).     

LC-MS and FT-IR characterization of amber artifacts

This work focuses on using analytical methods, such as Fourier transform Infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection to assess archaeological and geological amber. The main goal of this study is to apply the previously developed and optimized analytical methods in verifying criteria to ascribe and characterize the origin of materials found in archaeological sites. The proposed LC-MS method was successfully applied for the quantification of succinic acid content both in geological and archaeological samples of amber and offers excellent linearity between 0.1 and 5??g mL^?1. The developed FTIR method provided some criteria which is able to differentiate between Baltic and Romanian amber (Romanite) that furthermore validates on archaeological amber artefacts.      

Patination of historical stained windows lead cames from different European locations

Lead patination is a well-known phenomenon that occurs when lead is exposed to the atmosphere. A thin film mainly composed of insoluble lead salts is then formed on its surface, protecting lead against further corrosion. A study of the superficial patination of an ensemble of historical stained glass windows lead cames from different European locations (Belgium, Germany, Holland, Spain and Poland) and different chronologies (from 13th to 20th centuries) is reported in this paper. The main goals of the research were to characterise, both morphological and chemically, the patinas formed on their surfaces and to assess the weathering factors influencing the development of these patinas. Conventional optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive X-ray microanalysis (EDX) and micro-Raman spectroscopy were used to determine the composition of the patinas. The resulting data have proved to be very useful in establishing the degree of advance of the patination process, which seems to be directly influenced by the environmental conditions to which the lead cames were exposed rather than by chronology of the samples. The results have also provided outstanding data to make decisions in conservation/restoration issues of such historical materials.     

Vibrational spectroscopy to study degradation of natural dyes. Assessment of oxygen-free cassette for safe exposition of artefacts

An important issue connected with conservation chemistry is how to improve the storage and exposure conditions in order to suppress the fading and degradation of dyes and other components of paintings. Although the oxygen-free exposure cassettes are commonly known in museums, there is still lack of information in the literature about the effect of anoxic conditions on the degradation of dyes. This study is an attempt to start a database formation on the dyes degradation. Five commercial dyes (indigo, dragon’s blood, curcumin, madder, carminic acid) were submitted to accelerated ageing by exposure to intensive light in the visible range in both oxygen-free (anoxia) and -rich conditions. Degradation of the samples was investigated by several analytical techniques (attenuated total reflectance infrared spectroscopy, Raman spectroscopy, reflectance UV–Vis spectroscopy, X-ray fluorescence spectroscopy and optical microscopy). The conclusions are based on the estimators (derived from the determination of colour differences from Vis spectra and from the changes in FTIR and Raman vibrational bands intensity). According to them, only indigo, dragon’s blood and curcumin show greater stability in anoxic conditions in comparison with oxygen-rich ones while madder, carminic acid undergo greater degradation.