Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2.

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2-, CdHL-, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3-, whose formation constant values at infinite dilution were log ß = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm-3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.

In situ DRIFT, Raman, and XRF implementation in a multianalytical methodology to diagnose the impact suffered by built heritage in urban atmospheres.

This work addresses the evaluation of an innovative mutianalytical method to assess the conservation state of a fifteenth century palace house. With the goal of reducing the handicaps of field analysis, the in situ spectroscopic assessment, often based on the use of X-ray fluorescence and Raman spectrometers, was complemented by the use of diffuse reflectance infrared Fourier transform spectroscopy. In this manner, its usefulness as a diagnostic tool to discover the origin and mechanisms of the damage caused by atmospheric and infiltration water attacks were thoroughly examined. Moreover, the study was extended in the laboratory to increase the information obtained by nondestructive techniques. The results revealed a severe material loss caused by soluble salts. Thus, a noninvasive sampling method using cellulose patches was tested to study the amount and mobility of salts by means of ion chromatography. Finally, to establish the chemical degradation processes that are occurring in the palace, a chemometric analysis of the quantitative data as well as the construction of thermodynamic models was done to advise on the required restorative actions. Graphical Abstract The different phases of the multianalytical method to assess the conservation state of built heritage.

Raman spectra of the different phases in the CaSO4-H2O system.

Although it is known that the CaSO4/H2O system is formed by at least five different phases, this fact is not correctly documented in Raman spectroscopy studies. The main problem detected in the literature was the incorrect definition of the anhydrite, which produced the assignation of different spectra for a single compound. In this sense, two different spectra were clearly identified from the bibliography, which showed different main Raman bands at 1017 or 1025 cm(-1), although anhydrite could be present even as three different polymorphous species with different structures. A better understanding of the whole system obtained from a review of the literature allowed new conclusions to be established. Thanks to that revision and the development of different thermodynamical experiments by Raman spectroscopy, the Raman spectra of each phase were successfully identified for the first time. In this way, the main Raman bands of gypsum, bassanite, anhydrite III, anhydrite II and anhydrite I were identified at 1008, 1015, 1025, 1017 and 1017 cm(-1), respectively. To conclude this work, the contradictions found in literature were critically summarized.

Relevance of cross-section analysis in correct diagnosis of the state of conservation of building materials as evidenced by spectroscopic imaging.

In the present work the need to use cross-section analysis as a routine procedure to characterize physiochemical damage on building materials was evaluated using a combination of spectroscopic imaging techniques based on Raman spectroscopy, X-ray fluorescence spectroscopy (XRF), and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX). First, samples for cross-section analysis required special preparation to avoid the loss of soluble and weakly anchored compounds and thereby ensure the representativeness of the analysis. To this end, samples were dry drilled and fractured with a single blow rather than cut to avoid friction. Cross-section analysis allowed surface deposition (crusts and patinas) to be differentiated from penetrating pollution and the affected depth to be determined. Elemental and molecular distributions were obtained to establish the origin of the compounds/elements found. Moreover, establishing the depth reached by the pollutant, which depends on the material porosity, can help to determine the physicochemical form of the pollutant. Finally, SEM-EDX images allowed surface and internal cracks, as well as the causes of these physical stresses, to be identified. As a result, surface analysis alone was shown to lead to incomplete or even incorrect conclusions that can be avoided by using cross-section analysis as a routine procedure when assessing the state of conservation of building materials.

Towards a rational design of materials for the removal of environmentally relevant cations: polymer inclusion membranes (PIMs) and surface-modified PIMs for Sn2+ sequestration in aqueous solution.

This work is focused on the design and preparation of polymer inclusion membranes (PIMs) for potential applications for stannous cation sequestration from water. For this purpose, the membranes have been synthesized employing two polymeric matrices, namely, polyvinylchloride (PVC) and cellulose triacetate (CTA), properly enriched with different plasticizers. The novelty here proposed relies on the modification of the cited PIMs by selected extractants expected to interact with the target cation in the membrane bulk or onto its surface, as well as in the evaluation of their performances in the sequestration of tin(II) in solution through chemometric tools. The composition of both the membrane and the solution for each trial was selected by means of a D-Optimal Experimental Design. The samples such prepared were characterized by means of TG-DTA, DSC, and static contact angles investigations; their mechanical properties were studied in terms of tensile strength and elastic modulus, whereas their morphology was checked by SEM. The sequestering ability of the PIMs toward stannous cation was studied by means of kinetic and isotherm experiments using DP-ASV. The presence of tin in the membranes after the sequestration tests was ascertained by µ-ED-XRF mapping on selected samples.

Analytical assessment to develop innovative nanostructured BPA-free epoxy-silica resins as multifunctional stone conservation materials.

Bisphenol A (BPA)-free epoxy resins, synthesized from low molecular weight cycloaliphatic compounds, may represents promising materials for stone conservation due to their very appealing and tunable physico-chemical properties, such as viscosity, curing rate and penetration ability, being also easy to apply and handle. Furthermore, alkoxysilanes have been widely employed as inorganic strengtheners since they are easily hydrolysed inside lithic substrates affording SiO linkages with the stone matrix. Taking into account the advantages of these two classes of materials, this work has been focused on the development of innovative conservation materials, based on hybrid epoxy-silica BPA-free resins obtained by reaction of 1,4-cycloexanedimethanol diglycidylether (CHDM-DGE) with various siloxane precursors, i.e. glycidoxypropylmethyldiethoxysilane (GPTMS), tetraethyl orthosilicate (TEOS) and isobutyltrimethoxysilane (iBuTMS), using the 1,8-diaminooctane (DAO) as epoxy hardener. Thanks to Raman spectroscopy the synthesis processes have been successfully monitored, allowing the identification of oxirane rings opening as well as the formation of the cross-linked organic-inorganic networks. In accordance with the spectroscopic data, the thermal studies carried out by TGA and DSC techniques have pointed that GPTMS is a suitable siloxane precursor to synthesize the most stable samples against temperature degradation. GPTMS-containing resins have also shown good performances in the dynamic mechanical analysis (DMA) and in contact angle investigations, with values indicating considerable hydrophobic properties. SEM analyses have highlighted a great homogeneity over the entire observed areas, without formations of clusters and/or aggregates bigger than 45 µm, for the cited materials, confirming the efficiency of GPTMS as coupling agent to enhance the organic/inorganic interphase bonding. The variations provided by the incorporation of nanostructured titania, specifically synthesized, inside the epoxy-silica hybrids have been also evaluated. According to all the collected results, the hybrid materials here reported have proven to be promising multifunctional products for potential application in the field of stone conservation.

Multi-analytical methodology to diagnose the environmental impact suffered by building materials in coastal areas.

This work is focused on the development of an innovative multi-analytical methodology to estimate the impact suffered by building materials in coastal environments. With the aim of improving the in situ spectroscopic assessment, which is often based on XRF and Raman spectrometers, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was implemented in the diagnosis study. In this way, the additional benefits from DRIFT were compared to the usual in situ analyses of building materials, which often have interferences from fluorescence and reststrahlen effects. The studies were extended to the laboratory scale by µ-X-ray fluorescence (µ-XRF) cross-section mapping and ion chromatography (IC), and the IC quantitative data were employed to develop thermodynamic models using the ECOS-RUNSALT program, with the aim of rationalizing the behavior of soluble salts with variations in the temperature and the relative humidity (RH). The multi-analytical methodology allowed identification of the most significant weathering agents and classification of the severity of degradation according to the salt content. The suitability of a DRIFT portable device to analyze these types of matrices was verified. Although the Kramers-Kronig algorithm correction proved to be inadequate to decrease the expected spectral distortions, the assignment was successfully performed based on the secondary bands and intensification of the overtones and decreased the time needed for in situ data collection. In addition, the pollutants' distribution in the samples and the possible presence of dangerous compounds, which were not detected during the in situ analysis campaigns, provided valuable information to clarify weathering phenomena.

Applicability of a Diffuse Reflectance Infrared Fourier Transform handheld spectrometer to perform in situ analyses on Cultural Heritage materials.

This work studies the applicability of a Diffuse Reflectance Infrared Fourier Transform handheld device to perform in situ analyses on Cultural Heritage assets. This portable diffuse reflectance spectrometer has been used to characterise and diagnose the conservation state of (a) building materials of the Guevara Palace (15th century, Segura, Basque Country, Spain) and (b) different 19th century wallpapers manufactured by the Santa Isabel factory (Vitoria-Gasteiz, Basque Country, Spain) and by the well known Dufour and Leroy manufacturers (Paris, France), all of them belonging to the Torre de los Varona Castle (Villanañe, Basque Country, Spain). In all cases, in situ measurements were carried out and also a few samples were collected and measured in the laboratory by diffuse reflectance spectroscopy (DRIFT) in order to validate the information obtained by the handheld instrument. In the analyses performed in situ, distortions in the diffuse reflectance spectra can be observed due to the presence of specular reflection, showing the inverted bands caused by the Reststrahlen effect, in particular on those IR bands with the highest absorption coefficients. This paper concludes that the results obtained in situ by a diffuse reflectance handheld device are comparable to those obtained with laboratory diffuse reflectance spectroscopy equipment and proposes a few guidelines to acquire good spectra in the field, minimising the influence caused by the specular reflection.

Determination of the pigments present in a wallpaper of the middle nineteenth century: the combination of mid-diffuse reflectance and far infrared spectroscopies.

In this work the determination of the pigments present in a decorative wallpaper of the middle nineteenth century from the Santa Isabel factory (Vitoria-Gasteiz, Basque Country, Spain) has been performed by a combination of mid-Diffuse Reflectance Infrared Spectroscopy (DRIFT) and Far Infrared Spectroscopy (FIR) in transmission mode. The DRIFT is a powerful infrared technique that is not widely used in the analyses of artworks in spite of being especially adequate for powdered samples. In this mode, sample pretreatment is not required and the obtained spectra are easier to solve than those obtained in transmittance mode. Those pigments which are not active in the mid-infrared region may be determined easily by FIR. In the last decade, in the field of painted materials very few studies performed by far infrared spectroscopy and mid infrared spectroscopy in diffuse reflectance mode can be found. In most of them the researchers have used one of these techniques, but in no case the combination of both. As we demonstrate in this work, combining these two techniques a complete characterization of the wallpaper can be carried out. Small samples were collected from the wallpaper for the analysis of the rose, brown, yellow and blue colours. In this way, minium (Pb3O4), calcite (CaCO3), barium sulphate (BaSO4), prussian blue (Fe7C18N18), iron oxide yellow (α-FeOOH), vermillion (HgS) and carbon black pigment from organic origen were detected. Finally, the validation was carried out by XRF and Raman spectroscopy getting the same results as with the combination of diffuse reflectance infrared spectroscopy and far infrared spectroscopy.