0000000000178183
AUTHOR
F. Bosch Reig
Study of the formation of carbonyl compounds in edible oils and fats by 1H-NMR and FTIR
Abstract Oils and fats start decomposing from the moment they are isolated from their natural environment. Heating accelerates oxidative rancidity and frying at high temperatures produces thermal degradation with the formation of decomposition products, such as aldehydes, ketones, free acids and hydroxilic compounds that in high levels can be harmful to human health. The decomposition products formed up to 300°C were determined by means of 1 H-NMR spectroscopy and an FTIR spectroscopic method was developed for the quantification of carbonyl compounds generated during heating. The results show that there is a formation of carbonyl compounds starting at 150°C and when the sample was heated at…
Study and dating of medieval ceramic tiles by analysis of enamels with atomic absorption spectroscopy, X-ray fluorescence and electron probe microanalysis
Abstract This paper reports an analytical study of enamel on fragments of medieval tiles using atomic spectroscopy techniques — AAS, XRF and SEM/EDX. The samples came from a hermitage in the region of Valencia (Spain) and have different motifs, mainly floral ones in a wide variety of colors. A study of the soluble salts in the biscuits and mortar was carried out using AAS to determine their present capacity to produce efflorescence and the type of efflorescence. XRF was used to identify the oxides responsible for the different colors and the pigments used over large areas of the tiles (white and green). SEM/EDX was used to characterize the white and green and smaller areas of other colors. …
Analytical evaluation of polyunsaturated fatty acids degradation during thermal oxidation of edible oils by Fourier transform infrared spectroscopy
The oxidative deterioration of polyunsaturated fatty acids (PUFAs) in culinary oils and fats during episodes of heating associated with normal usage (80-300 degrees C, 20-40 min) has been monitored by Fourier transform infrared spectroscopy (FTIR). The thermal oxidation of PUFAs is a free radical chain reaction, in which hydroperoxides are generally recognized as the primary major products. Hydroperoxides of PUFAs are easily decomposed into a very complex mixture of secondary products with the decrease in unsaturation. The oxidative advance of PUFAs during heating was studied by the determination of unsaturation percentage at different temperatures and heating times. Oils frequently used in…
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…
Determination of unsaturation grade and trans isomers generated during thermal oxidation of edible oils and fats by FTIR
Abstract The oxidative deterioration of culinary oils and fats during episodes of heating associated with normal usage (80°C–300°C, 20–40 min) was monitored by FTIR spectroscopy. The thermal oxidation of polyunsaturated fatty acids during heating was studied by the determination of unsaturation percentage and trans isomers at various temperatures and heating times. Oils frequently used in food frying such as olive oil, sunflower oil, corn oil and seeds oil (sunflower, safflower and canola seed), and lard were studied. The Absorbance Correction Method is proposed to correct the spectral interference and allows the analytic use of signal which would not be initially valid for quantitative ana…
Correction parameters in X-ray fluorescence analysis applying the limit dilution method (LDM)
This paper is a study of the interelemental effect and its correction based on the mathematical model used to develop LDM in XRF analysis. A “compensation coefficient” is defined which is obtained from the quotient of the mass absorption coefficients of the problem and the standard (μs*/μp*). This coefficient compensates the effects produced by interactions between the analyt and the interferences and therefore acts as a correction factor for the interelemental effect within this theoretical model. The model itself establishes a simple relation of the “compensation coefficient” and the Y/H correction parameters for the unknown and the standard. An algorithm is proposed for calculating the “…
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.
A mathematical model based on the limit dilution method to obtain linear calibration curves which eliminate the matrix effect in quantitative analysis by X-ray fluorescence
Abstract We propose a mathematical model from an analytical application viewpoint inspired in the limit dilution method. The theoretical development of the model and its results are given. The model shows that there is a linear relation between the inverse of fluorescence intensity and the inverse of the dilution factor; each analytic system (sample, diluent and analyte) is characterised by a general linear function which is easily obtained. The analytical applications arising from this linearity are of great importance in X-ray fluorescence analysis. The following immediate applications are proposed: direct procurement of the total correction factor Y/H, rapid calculation of the fluorescen…
Determination of fluoride in rocks, soils, and fluoride-bearing minerals by separation using direct distillation in sulfuric acid medium and spectrophotometric analysis
Abstract An analytical method for fluoride determination in geological samples is proposed. It is based on a previous fluoride separation by distillation with a Teflon reactor. The variables that influence distillation quantitation (temperature, time, and acid concentration) are optimized. The influence of some species on fluoride recovery during distillation are studied, and conditions to avoid this influence are suggested. Fluoride determination is carried out by means of a spectrophotometric method [La(III)-F−-Alizarin complexone system] (N. T. Crosby, A. L. Dennis, and J. G. Stevens, Analyst (London), 1968, 93, 643–652). The method is applied to the analysis of soils, rocks, and fluorid…
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…
Evaluation of the interelemental effect in X-ray fluorescence analysis by the total addition method
An algorithm for quantifying interelemental effects in X-ray fluorescence techniques is developed. By applying an addition process, the ratio between the mass absorption coefficients of the analyte and the unknown sample (μi*/μs*) is calculated to correct the fluorescence intensity of the element to be determined and linearize the I-c calibration plot. This coefficient can be calculated graphically and numerically. The method is applied to the determination of tin in lead alloys with good results over wide concentration ranges.
FTIR quantitative analysis of calcium carbonate (calcite) and silica (quartz) mixtures using the constant ratio method. Application to geological samples.
A methodology for quantifying calcium carbonate (875 and 712 cm(-1)) and silica (798 and 779 cm(-1)) by FTIR spectroscopy applying the constant ratio method is proposed. The studied method is applied for quantitative analysis of calcite and quartz in geological samples. The suggested method uses potassium ferricyanide (2115 cm(-1)) as standard and samples are prepared as potassium bromide pellets, with statistically satisfactory results (relative standard deviation less than 5%). The influence of particle size (pulverised samples) on the accuracy of the results found by FTIR spectroscopy applying the constant ratio method has been studied. The granulometric study suggests that the homogenei…
Generalised H-point standard addition method for the isolation of the analyte signal from the sample signal when coelution of unknown compounds occurs in liquid chromatography.
The generalised H-point standard addition method (GHPSAM) is proposed for isolating the analytical signal of an analyte from the signal of an unknown sample. Samples containing two and three coeluting compounds have been analysed. The accuracy of the predictions depends on the shape of the analyte and interferent spectra but not on the degree of chromatographic overlap. This methodology involves the location of linear intervals for the unknown interference spectrum from the spectrum of the sample. Once the linear interval has been found the selection of three wavelengths within the interval will allow the cancellation of the signal of the unknown interferent. The method has been applied to …
Spectrophotometric determination of vitamin C using the copper(II)-nioxime-ascorbic acid system following stabilization in a propylene glycol medium
Abstract A spectrophotometric method for the determination of Vitamin C is proposed. The procedure is based on formation and stabilization of the ternary complex Cu(II)-nioxime-ascorbic acid in 80% ( v v ) propylene glycol-water medium. The method has a high degree of tolerance for the determination of ascorbic acid in the presence of other active substances or excipients likely to be present along with vitamin C in pharmaceutical formulations. The suggested method has proved to be rapid and precise and has been successfully applied to different commercial pharmaceutical preparations of vitamin C. Precision, measured on the relative standard deviation, did not exceed 0.73%.
Observations on the use of a sulfuric acid medium for As(V) to As(III) reduction in lodimetric titrations: Application to the determination of total arsenic
Abstract The use of a sulfuric rather than a hydrochloric acid medium for the reduction of As(V) to As(III) by iodide is proposed. Optimum conditions of acid concentration, amount of sodium hydroxide, and time and temperature are established to achieve quantitative reduction. The optimized reduction procedure was applied to the iodimetric determination of total arsenic and compared to a procedure that employs a hydrochloric acid medium. A systematic error of 0.04% was found for the method with a sulfuric acid medium opposed to 0.05% for the method with a hydrochloric acid medium in the reduction step. The proposed modified iodimetric method has been successfully used with some organic sampl…
Atomic-absorption spectrometric determination of calcium, magnesium and potassium in leaf samples after decomposition with molten sodium hydroxide
Abstract The decomposition of standard leaf samples of varied origin and nature by fusion with sodium hydroxide in an open system has been studied. The use of sodium nitrate as an auxiliary agent facilitated the mineralization of most of the samples. The solutions obtained were analysed for calcium, magnesium and potassium by flame atomic-absorption spectrometry. The method is fast and quite precise, with absolute standard deviations of 0.04–0.13, 0.002-0.03 and 0.04–0.12% for calcium, magnesium and potassium contents of O.8-5.0, 0.13–0.48 and 0.36–2.2% respectively. The limits of detection (μg/ml) in the determination step were 0.10 for calcium, 0.011 for magnesium, and 0.09 for potassium.
A chemometric study of the simultaneous determination of calcium and magnesium in natural waters
A method for the simultaneous spectrophotometric determination of calcium and magnesium in mineral waters with an FIA system is tested. The method is based on the reaction between the analytes and arsenazo(III) at pH 8.5. The calculations of the amounts of both analytes in the samples are carried out with the H-point standard addition method (HPSAM) for ternary mixtures, and with a partial least squares (PLS) model after a proper variable selection. The results obtained for the determination of calcium were comparable using both methods. The employment of the HPSAM brings to our attention the influence of the calcium concentration in the sample to the development of the reaction between mag…
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…
Analytical study by SEM/EDX and metallographic techniques of materials used in the iron production process during the iberian period
Abstract This work is the archaeometric study of different types of materials used in iron production in the Iberian Period (6th–2nd century b.c.). The materials were recovered in several archaeological digs (which makes it possible to date the archaeological remains) on different sites in the Levante area of the Iberian Peninsula. The samples selected for this study belong to different materials used in the ancient iron production process such as ores, slags, finished objects, etc. The use of scanning electron microscopy (SEM) is proposed to observe surface images of the samples to determine their morphological, microstructural and topographic characteristics to obtain valuable information…
H-point standard additions method for resolution of overlapped chromatographic peaks with a conventional fluorescence detector. Determination of phenol and cresols in waters
The H-Point Standard Additions Method (HPSAM) is proposed in order to resolve overlapping peaks in liquid chromatography by using a conventional fluorescence detector. The method uses as analytical signals the heights or the areas obtained at two previously selected emission wavelengths, and good results are obtained for highly overlapping peaks with highly overlapping fluorescence spectra. The principal benefits of the method are the ease of finding the required wavelengths, its insensitivity to changes in the retention time of the peak from one injection to another, and the possibility of using it in highly or only partially overlapping peaks. We have applied the method to the determinati…
Analysis of insoluble silicate: Decomposition with molten sodium hydroxide and determination of Zr(IV) with chloranilic acid in medium-strong acid
A rapid, accurate and precise method for the determination of zirconium in silicates is proposed. Insoluble or sparingly soluble samples are decomposed by means of molten sodium hydroxide. Chloranilic acid is employed as reagent for the spectrophotometric determination of Zr(IV). The limit of detection is 1.2×10−7 M and the relative standard deviation is 0.24%.
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…
EVALUATION OF THE COLOR OF SOME SPANISH UNIFLORAL HONEY TYPES AS A CHARACTERIZATION PARAMETER
Abstract The color of 7 types of Spanish unifloral honey from rosemary, orange blossom, lavender, eucalyptus, sunflower, heather, and honeydew was Investigated for Its potential use as a characterization parameter. Colors were estimated by visual comparison with a Lovlbond 1000 Instrument, the readings of which were transformed Into Pfund units. As an alternative method, the transmittances of liquid samples at selected wavelengths were measured, trlstlmulus values were calculated, and chromatic coordinates In the CIE-1931 (x,y,L) and CIE-1976 (L*a*b*) color spaces were determined. The correlation coefficient between x and the Pfund grading was 0.958, but visual comparisons proved to be less…
Study of binding media in works of art by gas chromatographic analysis of amino acids and fatty acids derivatized with ethyl chloroformate
The aim of this work is to identify proteinaceous and oil binding media used in paintings from art collections in the Region of Valencia (Spain). This information is extremely useful for conservation and restoration work. The proposed procedure involves protein and glyceride hydrolysis from sub-milligram samples by treatment with hydrochloric acid, followed by neutralization, partition with chloroform and derivatization with ethyl chloroformate (ECF) of both the aqueous and the organic phases. The ECF derivatives of amino acids and azelaic, myristic, palmitic and stearic acids are separated by capillary gas chromatography. Amino acids are mainly found in the aqueous phase and long chain fat…
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…
A taylor series model to evaluate the interelemental effects in X-ray fluorescence analysis, applied to the iron-zirconium-diluent system
A semi-empirical model has been developed to quantify the interelemental effects in X-ray fluorescence analysis. The measured X-ray fluorescence intensity has been expressed as a function of the different fluorescence elements composing the sample. this complex function has become an operative function via a Taylor series development. An explication has been given for the significance of the different terms of the series. These terms respond to mathematical functions known as characteristic functions for each chemical system. A parameter (B) has been defined which makes it possible to quantify the influence of the interelemental effect as a function of the analyte concentration (C) and that…