Resonance Raman imaging as a tool to assess the atmospheric pollution level: carotenoids in Lecanoraceae lichens as bioindicators.

Raman spectroscopy differentiation of carotenoids has traditionally been based on the ν 1 position (C = C stretching vibrations in the polyene chain) in the 1500-1600 cm(-1) range, using a 785 nm excitation laser. However, when the number of conjugated double bonds is similar, as in the cases of zeaxanthin and ß-carotene, this distinction is still ambiguous due to the closeness of the Raman bands. This work shows the Raman results, obtained in resonance conditions using a 514 mm laser, on Lecanora campestris and Lecanora atra species, which can be used to differentiate and consequently characterize carotenoids. The presence of the carotenoid found in Lecanoraceae lichens has been demonstrated to depend on the atmospheric pollution level of the environment they inhabit. Astaxanthin, a superb antioxidant, appears as the principal xanthophyll in highly polluted sites, usually together with the UV screening pigment scytonemin; zeaxanthin is the major carotenoid in medium polluted environments, while ß-carotene is the major carotenoid in cleaner environments. Based on these observations, an indirect classification of the stress suffered in a given environment can be assessed by simply analysing the carotenoid content in the Lecanoraceae lichens by using resonance Raman imaging.

Focused ultrasound solid-liquid extraction for the determination of organic biomarkers in beachrocks.

Beachrocks are consolidated coastal sedimentary formations resulting mainly from the relative rapid cementation of beach sediments by different calcium carbonate polymorphs. Although previous works have already studied the elemental composition and the mineral phases composing these cements, few of them have focused their attention on the organic matter present therein. This work describes an extraction methodology based on focused ultrasound solid-liquid extraction (FUSLE), followed by analysis using large volume injection (LVI) in a programmable temperature vaporizer (PTV) combined with gas chromatography-mass spectrometry (GC-MS) in order to determine organics such as polycyclic aromatic hydrocarbons (PAHs) and biomarkers (hopanes), which can increase and confirm the information obtained so far. This goal has been achieved after the optimization of the main parameters affecting the extraction procedure, such as, extraction solvent, FUSLE variables (amplitude, extraction time and pulse time) and also variables affecting the LVI-PTV (vent time, injection speed and cryo-focusing temperature). The developed method rendered results comparable to traditional extraction methods in terms of accuracy (77-109%) and repeatability (RSD<23%). Finally, the analyses performed over real beachrock samples from the Bay of Biscay (Northern Spain) revealed the presence of the 16 EPA priority PAHs, as well as some organic biomarkers which could increase the knowledge about such beachrock formation.

The problem of sampling on built heritage: a preliminary study of a new non-invasive method.

The relevance of a risk assessment of the built heritage was clearly justified due to the fact that it acts as a pollutant repository and hazardous pollutants have the capacity to penetrate into materials. However, the limitation of the sampling processes due to the high value of the built heritage makes a correct evaluation difficult. For that reason, in the present work, the potential of agar gels as non-invasive samplers of built heritage deterioration products, like crusts and patinas, was evaluated. Different gels of agar and Carbopol® (as control gel) were applied on these built surfaces considering several factors: the treatment time, the effectiveness of the addition of EDTA (ethylenediaminetetraacetic acid, C10H16N2O8) and its concentration and the use of a buffer at pH 7.5. All these factors were evaluated in order to determine the capacity of these gels as sampling systems under non-controlled atmospheric conditions. The results obtained in the assays were evaluated by visual examination, by evolution of pH and by the most important techniques used in the risk assessment analysis of the built heritage (Raman spectroscopy, scanning electron microscope (SEM)/energy dispersive X-ray (EDX) and inductively coupled plasma mass spectrometry (ICP-MS)). In this evaluation, the agar gels showed an intrinsic capacity as sampler with respect to the gel Carbopol® and thus, the best option between the studied gels consisted on agar gels with 2 % of EDTA and the longest application time. On the whole, the agar gels showed an interesting potential as non-invasive samplers of built heritage deterioration materials which should be studied more in depth.

Buildings as repositories of hazardous pollutants of anthropogenic origin.

In the present work the pollutant content of diverse building materials was evaluated by the combination of spectrometric and chromatographic techniques. A first non-destructive analysis carried out by µ-XRF and Raman spectroscopy revealed a high impact of pollutants, which reached depths higher than 6mm. The quantitative analyses pointed out that black crust as accumulation nucleus where concentration values up to 3408 mg/kg of lead, 752 mg/kg of chromium or 220 mg/kg of arsenic, high amounts of diverse sulphates and nitrates as well as substantial amounts of polycyclic aromatic hydrocarbons (PAHs) of a clear pyrolytic source were determined. On the other hand, samples without black crust showed also a surprising soluble salt content up to 5%. Polychlorinated biphenyls (PCB) were found to be absent in all material types. The chemometric analysis of the quantitative results revealed that the accumulation capacity and the subsequent pollutant content depends on the type of construction materials, being mortars the most susceptible.

Optimization of two methods based on ultrasound energy as alternative to European standards for soluble salts extraction from building materials.

The Italian recommendation NORMAL 13/83, later replaced by the UNI 11087/2003 norm, were used as standard for soluble salts extraction from construction materials. These standards are based on long-time stirring (72 and 2h, respectively) of the sample in deionized water. In this work two ultrasound based methods were optimized in order to reduce the extraction time while efficiency is improved. The instrumental variables involved in the extraction assisted by ultrasound bath and focused ultrasounds were optimized by experimental design. As long as it was possible, the same non-instrumental parameters values as those of standard methods were used in order to compare the results obtained on a mortar sample showing a black crust by the standards and the optimized methods. The optimal extraction time for the ultrasounds bath was found to be of two hours. Although the extraction time was equal to the standard UNI 11087/2003, the obtained extraction recovery was improved up to 119%. The focused ultrasound system achieved also better recoveries (up to 106%) depending on the analyte in 1h treatment time. The repeatabilities of the proposed ultrasound based methods were comparables to those of the standards. Therefore, the selection of one or the other of the ultrasound based methods will depend on topics such as laboratory facilities or number of samples, and not in aspects related with their quality parameters.

Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

Beachrock formation in temperate coastlines: examples in sand-gravel beaches adjacent to the Nerbioi-Ibaizabal Estuary (Bilbao, Bay of Biscay, North of Spain).

Beachrocks are coastal sedimentary formations resulting from a relative rapid cementation of beach sediments by the precipitation of carbonate cements. These lithified structures are not usually observed at temperate settings. The present work is focused on the occurrence of a significant intertidal cementation in sand-gravel beaches formed among 43°N latitude coastline, close to the Nerbioi-Ibaizabal estuary (Bilbao, Bay of Biscay, North of Spain). Raman micro-spectroscopy combined with SEM-EDX analyses and petrographic descriptions have been applied for the determination of the cement generations and the cemented materials compositions of the beachrock outcrops. In general terms, the cements described were: Cement Generation 1 (CG 1, aragonite, high-magnesium calcite and silicate mixtures), Cement Generation 2 (CG 2, aragonite) and Cement Generation 3 (CG 3, mixtures of CaCO(3) polymorphs and iron oxides). The rest of the interstitial porosity of the rocks appeared either empty or filled with heterogeneous cemented mixtures of previously reworked compounds. The mineralogy, the regular distribution and the isopachous character of the carbonate cements together with the accurate cementation at advanced seaward bands propose a possible marine-phreatic context for the beachrock formation. However, the impure cements and the materials covering the interstitial porosity seem to be the result of both, the weathering actions consequences and the surface alterations of specific grains. Moreover, the presence of modern cemented materials (e.g. slag, bricks and pebbles) suggest a recent formation of the phenomenon.

Classification and identification of organic binding media in artworks by means of Fourier transform infrared spectroscopy and principal component analysis.

Fourier transform infrared spectroscopy is a powerful analytical technique to study organic materials. However, in Cultural Heritage, since the sample under analysis is always a complicated matrix of several materials, data analysis performed through peak-by-peak comparisons of sample spectra with those of standard compounds is a tedious method that does not always provide good results. To overcome this problem, a chemometric model based on principal component analysis was developed to classify and identify organic binding media in artworks. The model allows the differentiation of five families of binders: drying oils, waxes, proteins, gums, and resins, taking into account the absorption bands in two characteristic spectral windows: C-H stretching and carbonyl band. This new methodology was applied in the characterization of binders in three kinds of artworks: papers of historical, archeological, and artistic value, easel paintings, and polychromed stone-based sculptures.

Micro-Raman spectroscopic identification of natural mineral phases and their weathering products inside an abandoned zinc/lead mine.

Mining activities provide a good source of minerals of different nature. On the one hand, the primary minerals for whose formation a geological time-scale is required. On the other hand, secondary minerals, formed from removed products after the earlier weathering and alteration states. These are characteristic of the local geology and the environment context that commonly appears due to the low chemical stability of their original primary minerals. This work shows how quickly the reactions promoting secondary minerals may have taken place, due to the fact that these were found in newly formed solid materials called efflorescences. To achieve this purpose, the sampling is crucial. It was carried out in such a way that tried to guarantee that the samples collected consisted in the very top soil matter (first 2 cm depth). Thus, unlike the deeper soil, the material analysed may have been newly formed due to the interactions that they had with the place weathering agents (i.e. air oxygen, humidity, and microbial activities). Raman spectroscopy has emerged as a good and fast non-destructive technique that provides molecular information of the local mineralogy without the need of any pre-treatment of the samples. At the same time, the work looked for information on the variety of non-stable lead and-or zinc containing minerals due to the possible health and environmental risks they convey. Among the different minerals identified, 16 were of primary nature while 23 may be classified as secondary minerals, probably formed in the last decades as the result of the extractive activities.

Spectroscopic evaluation of the environmental impact on black crusted modern mortars in urban-industrial areas.

A multianalytical characterisation of black crusted modern construction materials from buildings located in the Bilbao Metropolitan area (North Spain) was carried out. According to the mineral composition determined by Raman spectroscopy, calcite and hematite were the major compounds found while aragonite, limonite, rutile, quartz and some aluminosilicates such as obsidian or amazonite (KAlSi(3)O(8)) were also present in minor percentages. As deterioration products, gypsum and anhydrite were widely found not only in the surface but also in the inner part of strongly deteriorated samples. Coquimbite (Fe(2)(SO(4))(3)·9H(2)O) was identified as well in the most protected facade where high amounts of Fe, having probably an anthropogenic origin, were measured by micro X-ray fluorescence (µ-XRF). Zn was found to be in high amounts while Cu, Pb, Ti, Mn, Sr and K were identified as minor elements. Considering the non-expected concentrations found for some anthropogenic elements, a sequential extraction was carried out in order to determine their chemical form by means of ion chromatography and inductively coupled plasma mass spectrometry. The orientation of the facades, which had a different influence from rain washing and industrial and traffic impact, was shown to affect the accumulation of different compounds in the black crust. Finally, the MEDUSA software was used to simulate the reactions among the original compounds, deposited pollutants and the atmospheric acid gases in order to explain the presence of the decaying species found.

Portable Raman monitoring of modern cleaning and consolidation operations of artworks on mineral supports.

Any restoration performed on cultural heritage artworks must guarantee a low impact on the treated surfaces. Although completely risk-free methods do not exist, the use of tailor-made procedures and the continuous monitoring by portable instrumentation is surely one of the best approaches to conduct a modern restoration process. In this work, a portable Raman monitoring, combined sometimes with spectroscopic techniques providing the elemental composition, is the key analysis technique in the three-step restoration protocol proposed: (a) in situ analysis of the surface to be treated (original composition and degradation products/pollutants) and the cleaning agents used as extractants, (b) the thermodynamic study of the species involved in the treatment in order to design a suitable restoration method and (c) application and monitoring of the treatment. Two cleaning operations based on new technologies were studied and applied to two artworks on mineral supports: a wall painting affected by nitrate impact, and a black crusted stone (chalk) altarpiece. Raman bands of nitrate and gypsum, respectively, decreased after the step-by-step operations in each case, which helped restorers to decide when the treatment was concluded, thus avoiding any further damage to the treated surface of the artworks.

Raman spectroscopy after accelerated ageing tests to assess the origin of some decayed products found in real historical bricks affected by urban polluted atmospheres.

Bricks, together with stones and mortars, can be considered as one of the most important building materials that constitute our built heritage. Numerous factors which cause several decaying pathologies in bricks can be listed, but it should be emphasised that the most severe and damaging one is the wet and dry deposition of both combustion and greenhouse gases (CO(2), SO(x) and NO(x) mainly). For instance, after the impact of CO(2) and SO(x), the decayed products promoted in bricks are carbonates and sulphates. Once identified in all these kinds of salts in real samples, it is necessary to make sure that the aggressive atmospheric conditions are sufficient to promote the formation of these salts. Therefore, accelerated exposure test are a good alternative in order to simulate the formation of these decayed compounds and to predict the reactions that promote the decaying mechanism. In this work, brick samples manufactured at different firing temperatures following ancient methods were subjected to humidity/dryness, freeze/thaw, CO(2) and SO(2) (KESTERNICH DIN 50018) accelerated ageing tests followed by a Raman spectroscopy screening in order to verify the formation of sulphate and carbonate salts in bricks on accelerated conditions, simulating the damage caused by a polluted atmosphere throughout many years of exposure.

Thermodynamic and Raman spectroscopic speciation to define the operating conditions of an innovative cleaning treatment for carbonated stones based on the use of ion exchangers--a case study.

Thermodynamic and Raman spectroscopic speciation was used to define the operating conditions for an innovative cleaning treatment of the decayed carbonate-based stones using ion exchange technology. The conditioning process of the Lewatit OC1071 anion exchanger with EDTA (Y) was monitored by ionic chromatography. Characterisation of the initial (R-Cl) and the final (R2-H2Y) forms of the ion exchanger was carried out by dispersive Raman microprobe spectroscopy. The subtraction spectrum obtained between the chloride and the EDTA forms of the ion exchanger shows Raman bands at 1403, 1324, 1223, 1122, 932, 908, 591, 431 and 350 cm(-1), which agree with bands showed in the spectrum of the standard solution of the H2Y(2-) species. Therefore, this seems to be the EDTA species which takes part in the cleaning treatment performed by using resin poultices on black crusted limestone samples from an historical building.

Analytical diagnosis methodology to evaluate nitrate impact on historical building materials.

Nitrate salts have become of greater importance in the decay of materials from historical buildings due to changes in the environment. This work presents an analytical diagnosis methodology to evaluate the impact of nitrate salts in mortars and bricks, combining noninvasive and microdestructive analytical techniques together with chemometric and thermodynamic data analyses. The impact of nitrate salts cannot be well ascertained if other soluble salts are not taken into account. Therefore, the principal results from this work relate to nitrate salts but some results for other kinds of salts are included. Data from Raman microprobe spectroscopy and micro X-ray fluorescence (micro-XRF) are used to characterise the original composition and a first approximation of the nature of the decay compounds, mainly nitrates. The soluble salts are extracted and the anions and cations are quantified by means of ion chromatography with conductimetric detection for anions/cations and inductively coupled plasma mass spectrometry (ICP/MS) for cations. The values obtained allow two different data treatments to be applied. First, chemometric analysis is carried out to search for correlations among anions and cations. Second, thermodynamic modelling with the RUNSALT program is performed to search for environmental conditions of soluble salt formation. All the results are finally used to diagnose the impact of nitrates.

Spectroscopic characterisation of moonmilk deposits in Pozalagua tourist cave (Karrantza, Basque Country, North of Spain).

Composition of moonmilk deposits located in different zones of the tourist Dolomite Cave of Pozalagua (Karrantza, Basque Country, North of Spain) was established by Raman spectroscopy. The deposits were located in column bases and detached rocks near a gour full of water or a dripping zone. Hydromagnesite (Mg(5)(CO(3))(4)(OH)(2).4H(2)O) with a strong Raman band at 1116 cm(-1) and weaker ones at 1522vw, 1487vw, 1452vw, 756w, 727w, 466w, 434w, 371w, 327m, 291w, 258w, 247vw and 230 m cm(-1) was found as the main component of the moonmilk. Aragonite is the unique calcium carbonate compound that sometimes composes the moonmilk but always together with the hydromagnesite. Among non-carbonate minerals, some nitrates (nitrocalcite, niter, nitromagnesite, nitratine and gwihabaite) and sulphates (arkanite) were also identified as minor compounds. Most of the deposits were matt white and pasty, but occasionally some samples appear greyish on the surface. In these samples, carbon particles were also found, apart from the above, and Raman shift changes were observed in the hydromagnesite spectra. Apart from the elements involved in the mentioned minerals, Si, Fe, Mn, Zn and Ti were identified by X-ray microfluorescence as trace elements and the results were correlated with mineral compositions found by Raman measurements. Furthermore, quantification of the soluble salts of moonmilk deposits was carried out by ionic chromatography and the results were chemometrically treated to find correlations among soluble ions and the composition of the mineral phases spectroscopically characterised.

An integrated analytical approach to diagnose the conservation state of building materials of a palace house in the metropolitan Bilbao (Basque Country, North of Spain).

Raman microprobe spectroscopy and microX-ray fluorescence were used to analyse the original composition and degradation products of the limestone and the sandstones from the facades of one historical building. Carbon particles, gypsum (CaSO(4).2H(2)O) and some nitrate compounds were determined by Raman measurements, while elemental characterisation carried out by microXRF revealed the presence of lead, sulphur and copper as pollutants. On the one hand, the grey sandstone is the most deteriorated and in some cases pollutants reach 3 cm depth. On the other hand, quantification of soluble salts (chlorides, sulphates, nitrates, nitrites, fluorides and carbonates) was accomplished by ion chromatography. Chloride and sulphates are not significant soluble salts in the façades of the building, but the amount of nitrate is even 136 g kg(-1) in some of the most deteriorated samples and of 147 g kg(-1) in black-crusts. Finally, organic compounds (mainly PAHs) were characterised by GC-MS. Concentrations higher than 20 ppm of total PAHs were measured in the black-crusts of the rain-protected facades. The presence of certain PAHs indicated combustion of fuels as the main source of deterioration for the palace house building materials.

Analysis of bulk and inorganic degradation products of stones, mortars and wall paintings by portable Raman microprobe spectroscopy.

This work reports the use of a portable Raman microprobe spectrometer for the analysis of bulk and decaying compounds in carbonaceous materials such as stones, mortars and wall paintings. The analysed stones include limestone, dolomite and carbonaceous sandstone, gypsum and calcium oxalate, both mono- and dihydrated, being the main inorganic degradation products detected. Mortars include bulk phases with pure gypsum, calcite and mixtures of both or with sand, soluble salts being the most important degradation products. The pigments detected in several wall paintings include Prussian blue, iron oxide red, iron oxide yellow, vermilion, carbon black and lead white. Three different decaying processes have been characterised in the mortars of the wall paintings: (a) a massive absorption of nitrates that reacted with calcium carbonate and promoted the unbinding of pigment grains, (b) the formation of black crusts in the vault of the presbytery and (c) the thermodecomposition of pigments due to a fire.