Metal stearate distributions in modern artists' oil paints: surface and cross-sectional investigation of reference paint films using conventional and synchrotron infrared microspectroscopy.

Zinc oxide is a prevalent industrial-age pigment that readily reacts with fatty acids in oil-based paints to form zinc carboxylates. Zinc stearate aggregates are associated with deterioration in late nineteenth and twentieth century paintings. The current study uses both conventional and synchrotron Fourier transform infrared spectroscopy (FT-IR) to investigate metal carboxylate composition in a range of naturally aged artists' oil paints and reference paint film draw-downs. The paints contain zinc oxide alone or in combination with lead white, titanium white, and aluminum stearate and are prepared with linseed and safflower oils. Attenuated total reflectance (ATR)-FT-IR using the conventional source identifies marked differences in carboxylate profiles between exposed and protected surfaces in a large number of samples. Synchrotron FT-IR microspectroscopy of thin paint cross-sections maps metal carboxylate distributions at high spatial resolution and resolves broad concentration gradients and micrometer-scale phase separation of carboxylate species. Aluminum stearate, a common paint additive, is found to influence the distribution of zinc carboxylates more strongly than pigment composition or oil type. The presence of aluminum stearate results in higher concentrations and more pronounced separation of saturated C16 and C18 chain zinc carboxylates in the margin of paint nearest the polyester substrate. The presence of aluminum stearate in association with zinc oxide has a clear influence on zinc carboxylate formation and distribution, with potential implications for long term stability of vulnerable paintings.

SEM backscattered-electron images of paint cross sections as information source for the presence of the lead white pigment and lead-related degradation and migration phenomena in oil paintings.

Scanning electron microscopy backscattered-electron images of paint cross sections show the compositional contrast within the paint system. They not only give valuable information about the pigment composition and layer structure but also about the aging processes in the paint. This article focuses on the reading of backscatter images of lead white-containing samples from traditional oil paintings (17th-19th centuries). In contrast to modern lead white, traditional stack process lead white is characterized by a wide particle size distribution. Changes in particle morphology and distribution are indications of chemical/physical reactivity in the paint. Lead white can be affected by free fatty acids to form lead soaps. The dissolution of lead white can be recognized in the backscatter image by gray (less scattering) peripheries around particles and gray amorphous areas as opposed to the well-defined, highly scattering intact lead white particles. The small particles react away first, while the larger particles/lumps can still be visible. Formed lead soaps appear to migrate or diffuse through the semipermeable paint system. Lead-rich bands around particles, at layer interfaces and in the paint medium, are indications of transport. The presence of lead-containing crystals at the paint surface or inside aggregates furthermore point to the migration and mineralization of lead soaps.

Spectroscopic investigations on the depth-dependent degradation gradients of aged triterpenoid varnishes.

The depth-profiles of accelerated aged triterpenoid dammar and mastic varnishes, which had been uncovered by optimized KrF excimer laser ablation (248 nm, 25 ns), were examined by ultraviolet-visible (UV/VIS) spectrophotometry and attenuated total reflection (ATR) Fourier transform infrared (FT-IR) spectroscopy. The results reflect both the optical properties at the bulk (UV/VIS) and the surface (ATR/FT-IR) and establish the presence of degradation gradients across the depth of the degraded natural resin films. It is demonstrated that the UV part of the ambient radiation is absorbed by the deteriorated surface and that the optical densities of the aged varnish decrease as a function of depth. The absorbed UV wavelengths at the surface and the depth-wise reduction of light intensity result in a depth-dependent decrease in carbonyl absorbance and an increase in C-H bending vibration modes of methylene species pointing to structural modification in the triterpenoid mixture across depth.

MALDI-TOF mass spectrometry on cellulosic surfaces of fresh and photo-aged di- and triterpenoid varnish resins.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight mass spectrometry (MALDI-TOF-MS) on cellulosic surfaces is shown to be a suitable method for examining highly oxidized terpenoids, which are otherwise too difficult to determine by other techniques. By crystallization of a 2,5-dihydroxybenzoic acid (DHB) matrix and the sample solution on cellulose-coated thin layer chromatography(TLC) plates, spectra with good signal/noise ratios are obtained and no significant interferences due to matrix ions or cluster ions were produced, at least not in the range of m/z values of interest (>300 Da). The validity of the method was tested on natural di- and triterpenoid resins used as paint varnishes by Old Masters. The samples were analyzed before and after artificial light ageing. Di- and triterpenoid compounds, being very sensitive towards photo-oxidation, were found as oxidized molecules even in the raw resins and in the unexposed varnish layers. Artificial ageing simulating window-filtered daylight resulted in a stronger oxidation of the original terpenoids and the incorporation of up to six oxygen atoms per molecule could be demonstrated. Terpenoid dimers and their oxidation products were also detected.

Analytical imaging studies clarifying the process of the darkening of vermilion in paintings.

Imaging secondary ion mass spectrometry (SIMS) is applied for the first time to paint cross sections with degraded vermilion (red mercury sulfide) paint to cast new light on the well-known problem of its light-induced darkening. The static SIMS data are combined with light microscopic, electron microscopic studies and energy-dispersive X-ray analysis to identify and localize the various reaction products. The spatial distribution of atomic and molecular species in paint cross sections of the native vermilion and the reaction products leads to the formulation of a new hypothesis on the reaction mechanism of the photodegradation of vermilion where two black and white reaction products are formed sequentially. Under the influence of light, some of the vermilion (HgS) is converted into Hg(0) and S(0). In this process, the chlorine ions, present in the native vermilion, act as a catalyst. We propose that the Hg(0) is deposited on the surface of the remaining HgS as elementary mercury nanoparticles, which turns the vermilion black. Chloride, derived from an external source, is accumulating in the black phase. The metallic mercury and the remaining HgS react away with the excess of chloride. Two intermediate products and a white end product, mercuric chloride (HgCl2), are formed.

Effects of traditional processing methods of linseed oil on the composition of its triacylglycerols.

Different oil processing methods were performed, which included washing with water and treatment with lead-based driers, with and without heating to different temperatures, giving a set of 7 oils to be investigated. The effects of the traditional processing methods of linseed oil on its triacylglycerol (TAG) composition were studied, using the following analytical methods: high performance size exclusion chromatography (HPSEC), Fourier transform infrared spectroscopy (FTIR), high-performance liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry (HPLC-APCI-MS), direct temperature resolved mass spectrometry (DTMS), matrix assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS), and electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). A decrease of the initial cis-double bonds and the formation of trans-double bonds upon heating of the oils was observed. Heating a lead and oil mixture to 150 degrees C, or heating the oil alone to 300 degrees C led to the highest degree of oxidation. A difference was observed for the oxidation patterns for oils with and without the addition of lead. Furthermore, levels of oxygen incorporation were higher when lead was added to the oil. High temperature treatment of the oils resulted in an increased average molecular weight. The changes in the initial conformation of the double bond systems observed with FTIR were supported by HPLC-APCI-MS measurements that showed the formation of a number of new isomeric TAGs in the heated oil compared to freshly pressed, untreated oil. Oligomerisation up to hexamers was observed with HPSEC, and MALDI-TOF-MS. The formation of oligomers up to trimers only, however, was observed with ESI-FTICR-MS. Incorporation of oxygen was mainly observed with MALDI-TOF-MS and ESI-FTICR-MS whereas with DTMS and FTIR hardly any evidence was found for this.

Imaging secondary ion mass spectrometry of a paint cross section taken from an early Netherlandish painting by Rogier van der Weyden.

Static secondary ion mass spectrometry (SIMS) is introduced as an analytical technique for the examination of paint cross sections to obtain simultaneous information about the nature and distribution of pigments and the binding medium from a single sample. A sample taken from the virgin's blue robe in the panel painting The Descent from the Cross (Museo del Prado, Madrid) of the Early Netherlandish painter Rogier van der Weyden (1399/1400-1464) was selected for investigation. Data were compared with reference compounds and reference lead white linseed oil paint and egg tempera paint. The static SIMS technique gave position-sensitive mass spectra that were used to image the elemental distribution of pigments and the molecular signature of components of the oleaginous binding medium. SIMS ion images of sodium and aluminum superimposed with the blue pigment ultramarine and those of copper, lead, and calcium with the position of the mineral pigments of azurite, lead white, and chalk, respectively. Preserved monocarboxylic acids of palmitic and stearic acids present as fatty acids and fatty acid lead soaps pointed to the use of linseed oil as a binding medium. Images from the oleaginous binding medium fatty acids show a correlation with the three main paint layers. The observed palmitic/stearic acid ratios for the two ultramarine layers and azurite layers are 1.3, 1.4, and 1.8, respectively. Fatty acids and fatty acid soaps show highest ion yields near lead white, a mineral pigment that serves as a natural chemical drier and is proposed to act as a template for the initial grafting of the polyunsaturated triglycerides of the linseed oil. Almost no fatty acids were detected in other layers visible by light microscopy. The fatty acid lead soaps point toward a mature ionomeric oil paint system that developed over centuries. SIMS evidence for egg tempera, still used in the 15th century, is not detected in the paint cross section. SIMS images correlate well with SEM/EDX, FT-IR and light microscopic images and the SIMS spectral data additionally support the identification of pigment particles, lead soaps, and other binding medium components.

Direct-temperature mass spectrometric detection of volatile terpenoids and natural terpenoid polymersin fresh and artificially aged resins.

Electron impact (EI) ionization and ammonia chemical ionization (NH(3)/CI) direct-temperature mass spectrometry (DTMS) was used to characterize five natural terpenoid resins: dammar, mastic, colophony, Manila copal and sandarac. Compositional differences were highlighted by the identification of low molecular mass compounds, ranging from di- to triterpenoids, and polymeric components, based on polycadinene and polycommunic acid. Photo-ageing processes occurring under accelerated indoor and outdoor exposure conditions were also investigated. NH(3)/CI and tetramethylammonium hydroxide EI were applied to increase the sensitivity towards highly oxidized molecules. Oxidation and cross-linking reactions were found to affect mostly triterpenoid resins and diterpenoid abietane and pimarane molecules. Oxidation proceeds through a radical mechanism, generally starting from conjugated double bonds. Oxygen atoms are incorporated in the terpenoid structures in the form of alcohols, ketones and carboxylic acids. Oxidized cadinene oligomers released by pyrolytic degradation of the polycadinene fraction of dammar were detected even in unaged samples. Evidence is given indicating the occurrence of cleavages in the cross-linked polycommunic structure of aged sandarac and Manila copal. Bond scissions produce oligomeric fragments based on the communic acid structure and sufficiently volatile to be desorbed at low temperature in DTMS measurements.

Electron capture and collisionally activated dissociation mass spectrometry of doubly charged hyperbranched polyesteramides.

Electron capture dissociation (ECD) of doubly protonated hyperbranched polyesteramide oligomers (1100-1900 Da) was examined and compared with the structural information obtained by low energy collisionally activated dissociation (CAD). Both the ester and amide bonds of the protonated species were cleaved easily upon ECD with the formation of odd electron (OE(.+)) or even electron (EE(+)) fragment ions. Several mechanistic schemes are proposed that describe the complex ECD fragmentation behavior of the multiply charged oligomers. In contrast to studies of biomolecules, the present results indicate that consecutive cleavages induced by intramolecular H-shifts are significant for ECD and of less importance for low energy CAD. The capture of an electron by the ionized species results in fragmentation associated with a redistribution of the excess internal energy over the products and the subsequent bond cleavage. Low energy, multiple collision CAD is found to be a more selective dissociation method than ECD in view of the observation that only amide bonds are cleaved for most of the hyperbranched polymers examined with CAD in this study. ECD appears not to provide complementary structural information compared to CAD in the study of hyperbranched polymers, even though a significantly more complex ECD fragmentation behavior is observed. ECD is shown to be of use for the structural characterization of large oligomers that may not dissociate upon low energy CAD. This is a direct result of the fact that ECD produces ionized hyperbranched oligomers with a relatively high internal energy.

Identification of pigments in paint cross sections by reflection visible light imaging microspectroscopy.

A setup for reflection visible light imaging microspectroscopy (VIS-imaging) as well as its evaluation and application is described and tested. The spatial resolution of the system is approximately 1 microm at a spectral resolution of 4 nm. The optical contrast between different colored particles in the surface of a sample is optimized with a new image processing method for mapping of the distribution of the identified pigment particles. The potential of VIS-imaging in the study of paint cross sections obtained from paintings is explored. Spectra obtained from pigment particles in these cross sections result in classification or identification of several pigments. The investigated paint samples are challenging test cases, as they contain several colored materials with a very fine distribution. VIS-imaging can identify and map the most common traditional blue pigments, i.e., smalt, azurite, ultramarine, and indigo in 17th century oil paintings. Smalt can be identified even after complete discoloration. VIS-imaging analysis assisted in the identification and mapping of modern synthetic red and yellow pigments in a 20th century painting.

Isomer separation of hyperbranched polyesteramides with gas-phase H/D exchange and a novel MS(n) approach: DoDIP.

Two approaches are introduced that provide information about the isomeric composition of hyperbranched polyesteramides. The first approach is based on a novel tandem mass spectrometric (MS(n)) approach that allows the study of different types of isomeric structures by a separation based on their difference in appearance energy. The method is called DoDIP: dissociation of depleted ion populations. A first MS/MS step is used to fragment isomers with relatively low appearance energy. The isomers with higher appearance energy are fragmented in a second MS/MS step of higher energy. The second approach is based on gas-phase H/D exchange experiments that result in a bimodal isotopic distribution for oligomers X(n)D(n+1) of which one distribution corresponds to a type of isomeric structure that exhibits H/D exchange behaviour and the other to an isomeric structure that does not exhibit H/D exchange behaviour. X is a difunctional anhydride of phthalic acid (P), 1,2-cyclohexanedicarboxylic acid (C), succinic acid (S) or glutaric acid (G). D in X(n)D(n+1) is a trifunctional diisopropanolamine and n the degree of polymerization. The type of isomeric structure that does not exhibit H/D exchange behaviour has a non-alternating monomer sequence that contains an amine bond with a relatively high proton affinity. The other isomeric structure that does exhibit H/D exchange behaviour has an alternating monomer sequence containing only amide and ester bonds with relatively low proton affinity. Oligomer structures were confirmed with additional MS(2) experiments after H/D exchange. H/D exchange experiments on the fragments obtained after MS(2) of the parent ion show that next to previously postulated mechanisms for the cleavage of the ester and amide bond another reaction pathway must be operational. A new mechanism is introduced to explain the H/D exchange behaviour of the fragments that requires a cleavage of the amide bonds only. Two types of fragments are formed by this mechanism. One type is protonated due to the cleavage of the amide bond whereas the other type has an oxazolonium ion structure due to the loss of an additional H(2)O.

Identification of non-cross-linked compounds in methanolic extracts of cured and aged linseed oil-based paint films using gas chromatography-mass spectrometry.

Methanolic extracts of paint samples of different composition and age were qualitatively investigated by GC-MS using an on-column injector after off-line methylation or trimethylsilyl derivatisation, and on-line thermally assisted (trans)methylation with tetramethylammonium hydroxide using Curie-point pyrolysis-GC-MS. The combination of these three analytical strategies led to the identification of typical oxidation products of unsaturated fatty acids by interpretation of their mass spectrum. Some of the identified compounds have not been reported before. Both the off-line and on-line GC-MS strategy show series of short-chain fatty (di)acids and C16 and (oxidised) C18 fatty acids. The major advantage of the on-line pyrolysis-GC-MS approach is that chemical work-up is minimal and very quick. With this technique both the carboxylic acid functionalities, and hydroxyl groups are methylated. Young paint films are shown to contain relatively more oxidised C18 fatty acids and less diacids compared to older paints, which is indicative for the on-going oxidation processes within the paint. After trimethylsilylation, monoacylglycerols are detected indicative for hydrolytic processes, which reflect the relative distribution of the most prominent silylated fatty acids present. Relatively more C16 and C18 monoacylglycerols are found in young paints, whereas older paints contain higher amounts of monoacylglycerols of diacids.

Differences in relative growth rate in 11 grasses correlate with differences in chemical composition as determined by pyrolysis mass spectrometry.

Eleven grass species varying in potential relative growth rate (RGR) were investigated for differences in chemical composition by pyrolysis mass spectrometry. The spectral data revealed correlations between RGR and the relative composition of several biopolymers. Species with a low potential RGR contained relatively more cell wall material such as lignin, hemicellulose, cellulose, polysaccharide-bound ferulic acid and hydroxyproline-rich protein, whereas species with a high potential RGR showed relatively more cytoplasmic elements such as protein (other than those incorporated in cell walls) and sterols.