0000000000364820
AUTHOR
M.t. Doménech Carbó
FT-IR quantitative analysis of solvent mixtures by the constant ratio method
Abstract An analytical methodology to quantify compounds in complex mixtures by FTIR spectroscopy is proposed and the “Constant Ratio Method” (CRM) was developed. The addition of a standard to the sample allows us to establish a constant KMS characteristic of the Analyte/Standard system which can be employed as a quantification factor of the analyte in different samples . In the proposed method the measurements are independent of optical path length. This method has been successfully applied to quantify butylacetate and toluene in binary and tertiary samples and tertiary mixtures. Butylacetate/toluene/nujol have been resolved employing valeronitrile as standard, obtaining values for relativ…
Fourier transform infrared spectroscopy and the analytical study of sculptures and wall decoration
Abstract An analytical examination of sculpture and wall painting, including several wooden polychromed carvings from Valencian churches (15th–17th centuries) using FT-IR spectroscopy is described. The organic and inorganic compounds used in the works of art and the different artistic techniques used in each historical intervention carried out in the sculptures are identified. The analytical information obtained with this technique on organic and inorganic compounds is extremely useful in the preliminary studies necessary for diagnosis and to decide on the conservation process.
Quantitative electron probe microanalysis of metallic oxide mixtures applying an empirical calibration technique
Abstract An analytical procedure is proposed for the independent quantitative chemical analysis of each element in the presence of other elements in the matrix of a sample by Energy Dispersive Electron Probe Microanalysis. For this purpose, an empirical calibration technique (which we shall call here the JABO method), which studies the variation of the X-ray intensities in terms of the analyte concentration in a chemical system with a complex matrix, is established. The methodology consists of the modification of the unknown sample by addition of a diluent, an internal standard and the analyte itself (dilution-addition method). A mathematical model is proposed to calculate the K parameters …
Multi-elemental determination of heavy elements in plastics using X-ray fluorescence after destruction of the polymer by molten sodium hydroxide
In this paper a method is proposed for the multielemental analysis of Sb(III), Ba, Cd, Cr(III), Hg, Pb and As(III) in plastics, using X-ray fluorescence after alkaline decomposition and preconcentration by (co)precipitation. The organic matrix is destroyed by decomposition with sodium hydroxide melted in a silver crucible by the open system technique, using sodium nitrate as auxiliary oxidant. The variables which influence preconcentration are optimized: digestion time, pH, salinity, carrier and sodium diethyldithiocarbamate (DDTC) and sodium rhodizonate (R) as precipitants. The calibration curves were linear up to 200 μg of the element present, except for lead (150 μg) antimony(III) (100 μ…
Direct infusion mass spectrometry as a fingerprint of protein-binding media used in works of art
A direct infusion mass spectrometry method for the characterization of proteinaceous glues from binding media used in pictorial works of art prior to conservation or restoration treatment is proposed. Amino acids are released by acid hydrolysis and dissolved in a mixture of acidic water and ethanol. This mixture is directly infused into a mass spectrometer without any derivatization. The mass spectrometer is operated in positive ion electrospray mode (ESI-MS) to yield [M+H]+ ions for the amino acids. Relative amounts of each amino acid are calculated for each protein (beef and porcine gelatines, albumin, casein and egg). The analyzed proteins were satisfactorily distinguished. The method is…
Analysis of toxic elements in plastic components for toys. Multi-elemental determination by x-ray fluorescence
Abstract An x-ray fluorescence method is proposed for the multi-elemental determination of toxic elements in plastic articles for children, viz., Sb(III), Ba, Cd, Cr(III), Hg, Pb and As(III). Mineralization is achieved by using molten sodium hydroxide to decompose the organic matrix, with sodium nitrate as auxiliary oxidant. Stable solutions containing the chemical species for analysis are obtained. The species are separated from the solution by (co)precipitation, in a medium of NH+4-NH3 buffer (pH 8.5) with sodium diethyldithiocarbamate, sodium rhodizonate and Fe3+, which acts as a carrier. The precipitates deposited on filter-paper are placed in the x-ray spectrometer in fine layer morpho…
Characterization of proteinaceous glues in old paintings by separation of the o-phtalaldehyde derivatives of their amino acids by liquid chromatography with fluorescence detection.
A HPLC-fluorescence method for characterization of proteinaceous glues from binding media used in pictorial works of art prior to conservation or restoration treatment is proposed. Fluorescence derivatization of amino acids released by acid hydrolysis of standard proteins is studied. The derivatization reagent was o-phtalaldehyde with 2-mercaptoethanol as catalyst. Mobile phase was a programmed gradient among two eluents (water buffered at pH 5.8 wit 5% THF, and methanol) and is able to satisfactorily resolve the amino acid derivatives in 45min. Peak area ratios among amino acid derivatives and the leucine derivative are useful to characterize the proteins. The method shows good sensitivity…
Analysis of archaeological pottery by X-ray fluorescence spectrometry applying the limit dilution method
A method for correcting the intensity of x-ray fluorescence (limit dilution method) is proposed for the analysis of samples with a complex matrix such as ceramic materials of archaeological interest. This method corrects the interelement effects, resolving the wide deviations which occur in the quantitative results obtained by x-ray fluorescence without correction. The contents of sodium, magnesium, aluminium, silicon, potassium, calcium, titanium and iron in sixteen archaeological ceramic samples of different origins and from different locations were determined. The results obtained are comparable to the values obtained by chemical analysis. A statistical study of the data was carried out …
Characterization of waxes used in pictorial artworks according to their relative amount of fatty acids and hydrocarbons by gas chromatography.
A study attempted to characterize natural waxes used in pictorial works of art was carried out by means of gas chromatography. The analytical treatment requires prior hydrolysis of the waxes to release the fatty acids (FA) (myristic (myr), palmitic (pal), oleic (ole), stearic (ste), araquidic (ara), behenic (beh), lignoceric (lig), cerotic (cer)) from the main esters of the waxes. The formation of volatile derivatives of the fatty acids was carried out by derivatization with ethyl choroformate (ECF). This derivatization reagent was chosen due to the speed, safety and quantitativity of the reaction. The analyzed hydrocarbons were n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracos…
Identification of lipid binders in old oil paintings by separation of 4-bromomethyl-7-methoxycoumarin derivatives of fatty acids by liquid chromatography with fluorescence detection.
A HPLC-fluorescence method for identification of drying oils from binding media or protective film used in pictorial works of art prior to conservation or restoration is proposed. Fluorescence derivatization of fatty acids released by hydrolysis of structural drying oils is studied. The derivatization reagent was 4-(bromomethyl)-7-methoxycoumarin with 18-crown-6 as catalyst. Mobile phase was programmed from methanol-water (90:10 v/v) to methanol-water (100:0 v/v) in 25 min. The excitation and emission wavelengths were 325 and 395 nm, respectively. Under these chromatographic conditions, coumarin derivatives of myristic, palmitic, oleic and stearic acids were satisfactorily resolved. The met…
Identification of drying oils used in pictorial works of art by liquid chromatography of the 2-nitrophenylhydrazides derivatives of fatty acids.
A new HPLC-UV-Vis method for identification of drying oils from binding media or protective film used in pictorial works of art prior to conservation or restoration is proposed. Chromophore derivatization of fatty acids released by hydrolysis of structural drying oils is studied. The derivatization reagent selected was 2-nitrophenylhydrazine with 1-ethyl-3-(3-dimethyl animopropyl)carbodiimide hydrochloride/pyridine as catalyst. This reaction was carried out using microwave heating. Mobile phase was methanol/water/n-propanol/acetic acid (80:14:5:1) running in isocratic mode. Absorbance was measured at 400nm. In these conditions, hydrazides of myristic, palmitic, oleic, and stearic acids were…