Abstract: An adhesive conducting electrode material containing of graphite, biocompatible ion exchange polymer nafion® and commercial mesoporous TiO2 impregnated with horseradish peroxidase (HRP) is prepared and characterized by amperometric, UVvis and N2 sorption methods. The factors influencing the performance of the resulting biosensor are studied in detail. The optimal electrode material consists of 45% graphite, 50% impregnated HRPTiO2 and 5% nafion®. The optimum conditions for H2O2 reduction are an applied potential of 0.3 V and 0.1 mM hydroquinone. Sensitivity and limit of detection in the optimum conditions are 1 A M−1 cm−2 and 1 µM correspondingly. The N2 sorption results show that the pore volume of TiO2 decreases sharply upon adsorption of HRP. The preparation process of the proposed enzyme electrode is straightforward and potentially can be used for preparation of carbon paste electrodes for bioelectrochemical detections.

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: The darkening of lead chromate yellow pigments, caused by a reduction of the chromate ions to Cr(III) compounds, is known to affect the appearance of several paintings by Vincent van Gogh. In previous papers of this series, we demonstrated that the darkening is activated by light and depends on the chemical composition and crystalline structure of the pigments. In this work, the results of Part 2 are extended and complemented with a new study aimed at deepening the knowledge of the nature and distribution of Cr and S species at the interface between the chrome yellow paint and the nonoriginal coating layer. For this purpose, three microsamples from two varnished paintings by Van Gogh and a waxed low relief by Gauguin (all originally uncoated) have been examined. Because nonoriginal coatings are often present in artwork by Van Gogh and contemporaries, the understanding of whether or not their application has influenced the morphological and/or physicochemical properties of the chrome yellow paint underneath is relevant in view of the conservation of these masterpieces. In all the samples studied, microscopic X-ray fluorescence (mu-XRF) and X-ray absorption near edge structure (mu-XANES) investigations showed that Cr(III)-based alteration products are present in the form of grains inside the coating (generally enriched of S species) and also homogeneously widespread at the paint surface. The distribution of Cr(III) species may be explained by the mechanical friction caused by the coating application by brush that picked up and redistributed the superficial Cr compounds, likely already present in the reduced state as result of the photodegradation process. The analysis of the XANES profiles allowed us to obtain new insights into the nature of the Cr(III) alteration products, that were identified as sulfate-, oxide-, organo-metal-, and chloride-based compounds. Building upon the knowledge acquired through the examination of original paint samples and from the investigation of aged model paints in the last Part 4 paper, in this study we aim to characterize a possible relation between the chemical composition of the coating and the chrome yellow degradation pathways by studying photochemically aged model samples covered with a dammar varnish contaminated with sulfide and sulfate salts. Cr speciation results did not show any evidence of the active role of the varnish and added S species on the reduction process of chrome yellows.

Abstract: This study investigated concentration profiles of trace, rare earth and platinum group metals in fluvial sediments from the Pangani river basin (43,650 km2), one of the largest river basins in Tanzania, to assess its environmental quality. Sediment samples were collected in two distinct seasons from 12 representative sites of diverse land-use practices and characterised by ICP-MS after optimised microwave digestion. Ecological risks were assessed by evaluation of pollution index and comparison with legislated sediment quality guidelines (SQG). The results revealed contamination by some trace metals (e.g. Pb, V, Cu, Cr, Ni, Cd, As, Co, Mn and Zn) in concentrations ranging from 0.7 to 2940 mg kg−1, and four rare earth elements (Y, Ce, Nd, Yb) in concentrations ranging from 0.9 (Yb) to 500 mg kg−1 dry weight (Ce), which significantly exceeded the estimated background values at some stations. Palladium was the only platinum group element that was detected in quantifiable concentrations (0.33.5 mg kg−1). Concentrations of some trace metals exceeded the SQGs at some localised areas. Principal component analysis and multivariate correlations indicated geochemical characteristics of the area as the major control of metal concentrations and spatial variability. Organic matter and clay contents also played a significant role in metal distributions. Assessment of land-use practices upstream of the sampling locations was used to trace potential anthropogenic sources of metal enrichments, where highest levels were found in areas close to urban centres and agricultural activities. The study provides baseline data for future monitoring programs, and highlights the need for more comprehensive analysis involving a wider spatio-temporal scale and ecotoxicological risk assessment.

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: Previous investigations about the darkening of chrome yellow pigments revealed that this form of alteration is attributable to a reduction of the original Cr(VI) to Cr(III), and that the presence of sulfur-containing compounds, most often sulfates, plays a key role during this process. We recently demonstrated that different crystal forms of chrome yellow pigments (PbCrO4 and PbCr1xSxO4) are present in paintings by Vincent van Gogh. In the present work, we show how both the chemical composition and the crystalline structure of lead chromate-based pigments influence their stability. For this purpose, oil model samples made with in-house synthesized powders of PbCrO4 and PbCr1xSxO4 were artificially aged and characterized. We observed a profound darkening only for those paint models made with PbCr1xSxO4, rich in SO42 (x ≥ 0.4), and orthorhombic phases (>30 wt %). Cr and S K-edge micro X-ray absorption near edge structure investigations revealed in an unequivocal manner the formation of up to about 60% of Cr(III)-species in the outer layer of the most altered samples; conversely, independent of the paint models chemical composition, no change in the S-oxidation state was observed. Analyses employing UVvisible diffuse reflectance and Fourier transform infrared spectroscopy were performed on unaged and aged model samples in order to obtain additional information on the physicochemical changes induced by the aging treatment.

Abstract: Over the past years a number of studies have described the instability of the pigment cadmium yellow (CdS). In a previous paper we have shown how cadmium sulfide on paintings by James Ensor oxidizes to CdSO4 center dot H2O. The degradation process gives rise to the fading of the bright yellow color and the formation of disfiguring white crystals that are present on the paint surface in approximately 50 mu m sized globular agglomerations. Here, we study cadmium yellow in the painting “Flowers in a blue vase” by Vincent van Gogh. This painting differs from the Ensor case in the fact that (a) a varnish was superimposed onto the degraded paint surface and (b) the CdS paint area is entirely covered with an opaque crust. The latter obscures the yellow color completely and thus presents a seemingly more advanced state of degradation. Analysis of a cross-sectioned and a crushed sample by combining scanning microscopic X-ray diffraction (mu-XRD), microscopic X-ray absorption near-edge spectroscopy (mu-XANES), microscopic X-ray fluorescence (mu-XRF) based chemical state mapping and scanning microscopic Fourier transform infrared (mu-FT-IR) spectrometry allowed unravelling the complex alteration pathway. Although no crystalline CdSO4 compounds were identified on the Van Gogh paint samples, we conclude that the observed degradation was initially caused by oxidation of the original CdS pigment, similar as for the previous Ensor case. However, due to the presence of an overlying varnish containing lead-based driers and oxalate ions, secondary reactions took place. In particular, it appears that upon the photoinduced oxidation of its sulfidic counterion, the Cd2+ ions reprecipitated at the paint/varnish interface after having formed a complex with oxalate ions that themselves are considered to be degradation products of the resin and/or oil in the varnish. The SO42- anions, for their part, found a suitable reaction partner in Pb2+ ions stemming from a dissolved lead-based siccative that was added to the varnish to promote its drying. The resulting opaque anglesite compound in the varnish, in combination with the underlying CdC2O4 layer at the paint/varnish interface, account for the orange-gray crust that is disfiguring the painting on a macroscopic level. In this way, the results presented in this paper demonstrate how, through a judicious combined use of several microanalytical methods with speciation capabilities, many new insights can be obtained from two minute, but highly complex and heterogeneous paint samples.

Abstract: Potentiometric sensors were used to study molecular interactions in liquid environments, with sensorgram methodology. This is demonstrated with a lipophilic rubber-, and with a collagen based hydrogel sensor coating. The investigated molecules were promazine and tartaric acid respectively. The sensors were placed in a hydrodynamic wall jet system for the recording of sensorgrams. mV sensor responses were first converted to a signal, expressing the concentration of adsorbed organic ions. Using a linearization method, a pseudo first order kinetic model of adsorption was shown to fit the experimental results perfectly. Kass, kon and koff values were calculated.. The technique can be used over 4 decades of concentration, and it is very sensitive to low MW compounds as well as to multiply charged large biomolecules. This study is the first to demonstrate the application of potentiometric sensors as an alternative and complement to SPR methods.

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: This work shows the benefits of characterizing historic paintings via compositional and microtextural data from micro-X-ray diffraction (μ-XRD) combined with molecular information acquired with Raman microscopy (RM) along depth profiles in paint stratigraphies. The novel approach was applied to identify inorganic and organic components from paintings placed at the 14th century Islamic UniversityMadrasah Yusufiyyain Granada (Spain), the only Islamic University still standing from the time of Al-Andalus (Islamic Spain). The use of μ-XRD to obtain quantitative microtextural information of crystalline phases provided by two-dimensional diffraction patterns to recognize pigments nature and manufacture, and decay processes in complex paint cross sections, has not been reported yet. A simple Nasrid (14th century) palette made of gypsum, vermilion, and azurite mixed with glue was identified in polychromed stuccos. Here also a Christian intervention was found via the use of smalt, barite, hematite, Brunswick green and gold; oil was the binding media employed. On mural paintings and wood ceilings, more complex palettes dated to the 19th century were found, made of gypsum, anhydrite, barite, dolomite, calcite, lead white, hematite, minium, synthetic ultramarine blue, and black carbon. The identified binders were glue, egg yolk, and oil.

Abstract: Many western manuscripts were written using iron gall inks. These inks can damage the paper via two major mechanisms: (a) acid hydrolysis, enhanced by humidity, and (b) oxidative depolymerization provoked by the presence of oxygen and free iron(II) ions. The degradation of unsized Whatman paper impregnated with different combinations of iron sulfate, gallic acid, and gum arabic was studied at room temperature in order to assess the relative importance of each mechanism. The samples were stored in various environments including a dry and/or an oxygen-free atmosphere. The cellulose depolymerization was monitored by viscometry and related to changes in the oxidation state of iron, determined by X-ray absorption near-edge spectrometry. The results indicate that residual amounts of oxygen (less than 0.1%) promote cellulose depolymerization, whereas the level of relative humidity has no impact. The cellulose depolymerization also appears closely correlated to oxidative mechanisms. Regarding the oxidation of iron, it only occurs in the simultaneous presence of oxygen and moisture, suggesting the occurrence of rustlike oxidative mechanisms. Finally, the presence of gallic acid has a strong influence, which is only partially explained by its capacity to reduce iron(III) to iron(II).

Abstract: On several paintings by artists of the end of the 19th century and the beginning of the 20th Century a darkening of the original yellow areas, painted with the chrome yellow pigment (PbCrO4, PbCrO4·xPbSO4, or PbCrO4·xPbO) is observed. The most famous of these are the various Sunflowers paintings Vincent van Gogh made during his career. In the first part of this work, we attempt to elucidate the degradation process of chrome yellow by studying artificially aged model samples. In view of the very thin (1−3 μm) alteration layers that are formed, high lateral resolution spectroscopic methods such as microscopic X-ray absorption near edge (μ-XANES), X-ray fluorescence spectrometry (μ-XRF), and electron energy loss spectrometry (EELS) were employed. Some of these use synchrotron radiation (SR). Additionally, microscopic SR X-ray diffraction (SR μ-XRD), μ-Raman, and mid-FTIR spectroscopy were employed to completely characterize the samples. The formation of Cr(III) compounds at the surface of the chrome yellow paint layers is particularly observed in one aged model sample taken from a historic paint tube (ca. 1914). About two-thirds of the chromium that is present at the surface has reduced from the hexavalent to the trivalent state. The EELS and μ-XANES spectra are consistent with the presence of Cr2O3·2H2O (viridian). Moreover, as demonstrated by μ-XANES, the presence of another Cr(III) compound, such as either Cr2(SO4)3·H2O or (CH3CO2)7Cr3(OH)2 [chromium(III) acetate hydroxide], is likely.

Abstract: We have investigated the plasma processes in an atmospheric pressure glow discharge (APGD) in He used for analytical spectrometry by means of fluid and Monte Carlo (MC) simulations. Typical results include the potential and electric field distributions in the plasma, the density profiles of the various plasma species throughout the discharge, the mean electron energy, as well as the rates of the various collision processes in the plasma, and the relative importance of the different production and loss rates for the various species. The similarities and differences with low-pressure glow discharges are discussed. The main differences are a very small cathode dark space region and a large positive column as well as the dominant role of molecular ions. Some characteristic features of the APGD, such as the occurrence of the different spatial zones in the discharge, are illustrated, with links to experimental observations.