Abstract: The study of materials in cultural heritage artifacts and micro-samples benefits from diagnostic techniques based on intense radiation sources, such as synchrotrons, ion-beam accelerators and lasers. While most of the corresponding techniques are classified as non-destructive, investigation with photons or charged particles entails a number of fundamental processes that may induce changes in materials. These changes depend on irradiation parameters, properties of materials and environmental factors. In some cases, radiation-induced damage may be detected by visual inspection. When it is not, irradiation may still lead to atomic and molecular changes resulting in immediate or delayed alteration and bias of future analyses. Here we review the effects of radiation reported on a variety of cultural heritage materials and describe the usual practice for assessing short-term and long-term effects. This review aims to raise awareness and encourage subsequent research activities to limit radiation side effects.

Abstract: Museum staff usually relies on a proven combination of X-ray radiography (XRR) and infrared reflectography (IRR) to study paintings in a non-destructive manner. In the last decades, however, the research toolbox of heritage scientists has expanded considerably, with a prime example being macro X-ray fluorescence (MA-XRF), producing element-specific images. The goal of this article is to illustrate the added value of augmenting MA-XRF with pulse phase thermography (PPT), a variant of active infrared thermographic imaging (IRT), which is an innovative diagnostic method that is able to reveal variations between or in materials, based on a different response to minor fluctuations in temperature when irradiated with optical radiation. By examining three 16thand 17th-century panel paintings we assess the extent in which combined MA-XRF and PPT contributes to a better understanding of two commonly encountered interventions to panel paintings: (a) Anstuckungen (enlargement of the panel) or (b) substitutions (replacement of part of the panel). Yielding information from different depths of the painting, these two techniques proved highly complementary with IRR and XRR, expanding the understanding of the build-up, genesis, and material history of the paintings. While MA-XRF documented the interventions to the wooden substrate indirectly by revealing variations in painting materials, paint handling and/ or layer sequence between the original part and the extended or replaced planks, PPT proved beneficial for the study of the wooden support itself, by providing a clear image of the wood structure quasi-free of distortion by the superimposed paint or cradling. XRR, on the other hand, revealed other features from the wood structure, not visible with PPT, and allowed looking through the wooden panels, revealing e.g. the dowels used for joining the planks. Additionally, IRR visualised dissimilarities in the underdrawings. In this way, the results indicate that PPT has the potential to become an acknowledged add-on to the expanding set of imaging methods for paintings, especially when used in combination with MA-XRF, IRR and XRR.

Abstract: The measurement of the ratio of stable isotopes of carbon (13C/12C expressed as a δ13C) in the individual components of a sample may be used as a means to identify the origin of these components. This article reviews the approaches and reports on the successes and failures of source identification and apportionment of Polycyclic Aromatic Hydrocarbons (PAHs) with the use of compound-specific isotope analysis (CSIA). One of the conditions for a precise and accurate analysis of isotope ratios with the use of GC-C-IRMS is the need for well separated peaks, with no co-elutions, and reduced unresolved complex mixture (UCM). Additionally, special care needs to be taken for an investigation of possible isotope fractionation effects introduced during the analytical treatment of samples. With the above-mentioned problems in mind, this review discusses in detail and compares current laboratory methodologies, mainly in the extraction and subsequent clean-up techniques used for environmental samples (air particulate matter, soil and sediments). Sampling strategies, the use of isotopic internal standards and the ranges for precision and accuracy are also reported and discussed.

Abstract: Ion chromatographic (IC) methods have been compared in order to achieve an optimal separation of fluoride, acetate and formate under various elution conditions on two formerly introduced analytical columns (i and ii) and a novel one (iii): (i) an IonPac AS14 (250 mm × 4 mm I.D.), (ii) Allsep A-2 (150 mm × 4.6 mm I.D.), and (iii) an IC SI-50 4E (250 mm (length) × 4 mm (internal diameter – I.D.)). The IC conditions for the separation of the anions concerned were optimized on the IC SI-50 4E column. A near baseline separation of these anions was attained on the IonPac AS14, whereas the peaks of fluoride and acetate could not be resolved on the Allsep A-2. A baseline separation for the three anions was achieved on the IC SI-50 4E column, when applying an eluent mixture of 3.2 mmol/L Na2CO3 and 1.0 mmol/L NaHCO3 with a flow rate of 1.0 mL/min. The highest precision of 1.7, 3.0 and 2.8% and the best limits of detection (LODs) of 0.014, 0.22 and 0.17 mg/L for fluoride, acetate and formate, respectively, were obtained with the IC SI-50 4E column. Hence, this column was applied for the determination of the acetic and formic acid contents of air samples taken by means of passive gaseous sampling at the Metropolitan Museum of Art in New York, USA. Atmospheric concentrations of acetic and formic acid up to 1050 and 450 μg/m3, respectively, were found in non-aerated showcases of the museum. In galleries and outdoors, rather low levels of acetic and formic acid were detected with average concentrations of 50 and 10 μg/m3, respectively. The LOD data of acetate and formate on the IC SI-50 4E column correspond to around 0.5 μg/m3 for both acetic and formic acid in air samples.

Abstract: For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 ìm particle size), Allsep A-2 (7 ìm particle size), and IC SI-50 4E (5 ìm particle size). A complete baseline separation for all analyzed anions (i.e., F−, acetate, formate, Cl−, NO2−, Br−, NO3−, HPO42− and SO42−) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na2CO3 and 1.0 mM NaHCO3 with a flow rate of 1.0 mL min−1. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na2CO3 plus 1.0 mM NaHCO3 with a flow rate of 1.2 mL min−1. Therefore, it was necessary to adapt a second run with a 2.0 mM Na2B4O7 solution as an eluent under a flow rate of 0.8 mL min−1 for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na2CO3 plus 1.5 mM NaHCO3 with a flow rate of 1.6 mL min−1, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L−1 for F−, Ac−, For−, Cl−, NO2−, Br−, NO3−, HPO42− and SO42−, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.

Abstract: Laser-assisted plasma spectrometry is a palette of analytical techniques (L-OES, LA-ICP-MS) capable of fast spatially-resolved elemental analysis in the micrometer range. For fast estimation of the occurrence in steel samples of non-metallic inclusions, which degrade the material's technical properties, simultaneous OES detection and sequential ICP-MS detection were compared. Histograms were obtained for the intensity distribution of the acquired signals (laser pulse statistics). The skewness coefficient of the histograms for Al (indicator of non-metallic inclusions) was found to be clearly dependent on the fraction of non-metallic inclusions in the case of scanning L-OES. For LA-ICP-MS less clear dependence was observed, which was influenced by the acquisition characteristics. In fact, less measurement throughput limited for LA-ICP-MS the counting statistics to an extent that overrides the benefit of higher detection power as compared to L-OES. (c) 2006 Elsevier B.V. All rights reserved.

Abstract: In order to obtain full information coverage on melt inclusions in Martian meteorites (subgroup nakhlites) complementary micro-analytical techniques were used, i.e. focused ion beam, transmission electron microscopy and laser ablation. Using focused ion beam several lamellae for transmission electron microscopy were prepared and secondary electron images of cross-sections could be acquired. Laser ablation-inductively coupled plasma mass spectrometry analyses were performed on selected inclusions to obtain mass-oriented bulk composition of inclusions at depth. The differences in composition between melt inclusions in olivine and augite crystals would suggest a xenocrystic origin for olivine. Furthermore, electron diffraction patterns clearly indicated that the SiO2-rich phase in inclusions from augite in meteorites from Northwest Africa site is re-crystallized, whereas it is still vitreous in the inclusions from Nakhla sampling site. Therefore, different post-entrapment evolutions were active for the two nakhlite meteorite sets, the Nakhla and the NWA817 set. Melt inclusions in Nakhla olivine presented alteration veins, which were presumably produced before their landing on Earth. If this is the case, this would indicate a alteration stage already on Mars with all the consequence in terms of climate history. Melt inclusions in Nakhla augite resulted unaffected by any alteration or modification following the entrapment, and therefore represent the best candidate to indicate the pristine magma composition. (c) 2005 Elsevier B.V. All rights reserved.

Abstract: Two common procedures for wet destruction of biological materials for subsequent determination of selenium have been investigated. Rat organs and biological fluids were endogenously labelled with 75Se to monitor losses during the procedures. Addition of nitric and perchloric acids with gradual heating up to 210° seemed to be the best method: at this temperature the labelled selenium was still recovered quantitatively, and the destruction was fast and efficient.

Abstract: Relative sensitivity factors for determination of 41 elements by spark-source mass-spectrometry have been measured. The samples were pressed into graphite electrodes and ionized with a radiofrequency spark. The mass spectra were recorded on a photoplate and the resulting data processed by a computer. Indium was used as standard and the relative sensitivity factors for both singly- and doubly-charged ions were determined with reference to the singly-charged indium ion, with an overall error of 30%. The mean analysis precision was 16%.