Method For Multielement Analysis Research Articles

Characterization of soils around a former chemical plant in Braila, SE Romania, using high performance atomic techniques (EDXRF, AAS, ICP-MS)

This paper presents the problem of soil pollution in the vicinity of a former chemical plant, given that production activity was stopped for more than thirty years ago. The old chemical plant was located in the southern part of Braila town, SE Romania, just a few kilometers from the left bank of the Danube River. Prior to 1990, there was a significant production of industrial chemical goods, such as sulfuric acid, carbon dioxide for synthetic fibers, chlorine gas and hydrochloric acid obtained by electrolysis processes with mercury electrodes and heavy metal catalysts (Cd, Ni, Zn), sodium sulfide and sulphate, etc. For the good development of the experimental program, a number of 10 soil samples were collected from the north, northwest, west, southwest and south of the former chemical plant. The multi-element analysis method used to determine the trace elements in the soil samples was energy-dispersive X-ray fluorescence spectrometry (EDXRF), using a Genius XRF portable spectrometer manufactured by Skyray Instruments Inc., equipped with a large surface Si with a Be window and a 40 kV/100 µA miniature X-ray tube excitation source with Ag target. The spectrometric system has an energy resolution up to 139 eV, and the detection limits of the order of ppm. A total of 21 chemical elements were identified in the target soil samples, such as: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Hg, Rb, Sr, Y, Zr, Nb, Mo, Sn, Sb, Pb. The compositional analyses of contaminated industrial soils were completed by using the AAS and ICP-MS high performance and selectivity techniques.

Impurity Elements Determination in High Purity Gold by Using LA-ICP-MS

The various impurities in high purity gold directly affect the quality and value of gold, and which concentration is usually ultra-low. The laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a quasi-non-destructive multi-elemental analytical method with low detection limits, high sensitivity and specificity. In this study, we introduce this method to detect impurity elements of 99.999% high purity gold through optimizing the parameters of laser energy density, repetition rate, and crater diameter. The concentration of 20 impurities were determined based on standard curve method, independently verified by glow discharge mass spectrometry (GD-MS) and inductively coupled plasma mass spectrometry (ICP-MS). The result shows the quantitative method was successfully used to the determination of impurity elements in high purity gold with the benefits of quasi-non-destruction, simplicity, real-time and green.

Ultrasound-Assisted Enzymatic Extraction Method for Multi-element Analysis of Rice

An ultrasound-assisted enzymatic extraction followed by a diluted acid washing was introduced into the multi-element analysis of rice samples. The recoveries of the elements including As, Cd, Mn, and Zn were evaluated by inductively coupled plasma mass spectrometry. The experimental parameters including enzyme type, enzyme dosage, ultrasound power, and duration of ultrasonication were investigated. The optimized condition was pancreatin with the dosage of 6.75 mg enzyme to 30-mg rice and ultrasonication for 5 min with the power of 800 W. The whole extraction procedure can be accomplished in 20 min. Three certified reference rice samples (GBW (E) 100348, GBW10043, and GBW10044) were used for method verification. The recoveries of As, Cd, Mn, and Zn ranged from 82.2 to 97.3%. The relative standard deviations of the four elements were all lower than 10%. Finally, the present method was successfully applied in the multi-element analysis of real samples.

Towards single-cell ionomics: a novel micro-scaled method for multi-element analysis of nanogram-sized biological samples

BackgroundTo understand processes regulating nutrient homeostasis at the single-cell level there is a need for new methods that allow multi-element profiling of biological samples ultimately only available as isolated tissues or cells, typically in nanogram-sized samples. Apart from tissue isolation, the main challenges for such analyses are to obtain a complete and homogeneous digestion of each sample, to keep sample dilution at a minimum and to produce accurate and reproducible results. In particular, determining the weight of small samples becomes increasingly challenging when the sample amount decreases.ResultsWe developed a novel method for sampling, digestion and multi-element analysis of nanogram-sized plant tissue, along with strategies to quantify element concentrations in samples too small to be weighed. The method is based on tissue isolation by laser capture microdissection (LCM), followed by pressurized micro-digestion and ICP-MS analysis, the latter utilizing a stable µL min−1 sample aspiration system. The method allowed for isolation, digestion and analysis of micro-dissected tissues from barley roots with an estimated sample weight of only ~ 400 ng. In the collection and analysis steps, a number of contamination sources were identified. Following elimination of these sources, several elements, including magnesium (Mg), phosphorus (P), potassium (K) and manganese (Mn), could be quantified. By measuring the exact area and thickness of each of the micro-dissected tissues, their volume was calculated. Combined with an estimated sample density, the sample weights could subsequently be calculated and the fact that these samples were too small to be weighed could thereby be circumvented. The method was further documented by analysis of Arabidopsis seeds (~ 20 µg) as well as tissue fractions of such seeds (~ 10 µg).ConclusionsThe presented method enables collection and multi-element analysis of small-sized biological samples, ranging down to the nanogram level. As such, the method paves the road for single cell and tissue-specific quantitative ionomics, which allow for future transcriptional, proteomic and metabolomic data to be correlated with ionomic profiles. Such analyses will deepen our understanding of how the elemental composition of plants is regulated, e.g. by transporter proteins and physical barriers (i.e. the Casparian strip and suberin lamellae in the root endodermis).

Development and validation of a method for multielement analysis of apatite by total-reflection X-ray fluorescence spectrometry

Apatite group of minerals incorporates a large range of trace metals such as Sr, Y, U, Th, as well as the rare earth elements, that allows obtaining useful information on their genesis and could be used in several applications in geology and geochemistry. In this study, a new method for the multielement analysis of apatite using total-reflection X-ray fluorescence spectrometry (TXRF) was developed. The acid digestion procedure was chosen as an optimal sample preparation with the capability to analyze a low sample amount (~5–10 mg). The validation of the method passed through the combination of procedures: analysis of Durango and Otter Lake well-known apatite samples; using inductively coupled plasma mass spectrometry and wavelength-dispersive X-ray fluorescence spectrometry as reference analytical methods; assessment of the measurement uncertainty. The proposed TXRF method is advantageous in being fast, cheap and simple for the multielement analysis of apatite with high accuracy.

Validation Procedure for a Multi-Element Analytical Method Aiming at Dietary Intake Estimation

Total diet study (TDS) is a useful way to estimate the dietary intake of hazardous and chemical substances. Regarding the analysis performed in TDS, international guidelines published by the World Health Organization, recommend selecting and confirming the validity of suitable analytical methods to achieve the purpose of TDS. However, concrete procedures and/or approaches for confirming the validity of suitable methods have yet to be established. In the present study, we aimed to develop samples, referred to as SEMPs; Samples to estimate methods performance, that can be used to evaluate the performance of the analytical methods applied to the composite samples prepared in TDS. The concentrations of 14 kinds of elements, including hazardous substances such as arsenic, lead, and cadmium, in SEMPs were measured for use in the validation of a multi-element analytical method for estimating dietary intake. After examining the appropriate amount of relevant elements added to the samples, we established a performance evaluation procedure by repeatedly analyzing five fortified and non-fortified SEMPs each.

Total reflection X-ray fluorescence

Abstract Total reflection X-ray fluorescence (TXRF) spectrometry is a non-destructive and surface sensitive multi-element analytical method based on energy dispersive X-ray fluorescence spectrometry with detection limits in the lower picogram range. It utilizes the total reflection of the primary X-ray beam at or below the critical angle of incidence. At this angle, the fluorescence intensity is substantially enhanced for samples present as small granular residue or as thin homogenous layer deposited at the surface of a thick substrate. Generally, two types of application exist: micro- and trace-analysis as well as surface and thin-layer analysis. For micro- and trace-analysis, a small amount of the solid or liquid sample is deposited on an optically flat substrate, typically quartz or polycarbonate. The dried residue is analyzed at a fixed angle setting slightly below the critical angle. Quantification is carried out by means of internal standardization. For surface and thin-layer analysis, the surface of an optically flat substrate is scanned. Variations of the incident angle of the primary X-ray beam provide information about the type and sometimes also the amount of material present at or slightly below the surface of the substrate. Major fields of application are environmental samples, biological tissues, objects of cultural heritage, semiconductors and thin-layered materials and films.

Optimization of Am–Be millicuries neutron source in a small volume cylindrical water tank for NAA

The neutron activation analysis (NAA) is a very powerful method for multi-element analysis of samples. NAA technique needs to be developed for low neutron flux in millicuries using the 241Am-Be neutron source. To optimize sample and neutron source geometry for maximum γ-ray yield for neutron activation analysis. Gamma ray neutron activation analysis (NAA) has been set up where a 50-millicurie Am-Be neutron source is available. In this experimental setup, the neutron source is placed at the center of a cylindrical water tank of 40 x 40 cm in xyz plan, and thermal neutrons are produced at a distance of 1.2 cm from the source. The system is used for the activation analysis of sodium carbonate, sodium chloride and copper with the gamma ray emissions of 1.37, 1.73, 2.25 and 2.76 MeV for 24Na and 0.511 MeV for 64Cu having half lives of 15 hrs and 12.9 hrs, respectively. The thermal neutron activation analysis has been demonstrated by placing the samples at about 1.2 cm from the neutron source. HPGe and 3x3 inch NaI(Tl) gamma ray spectrometers have been used for the gamma ray spectrometry of these activated samples with the use of a Marinelli beaker. The geometry of the sample with respect to the neutron source has been optimized for the maximum γ-ray yield in NAA. The geometry of the sample with respect to the neutron source has been optimized for the maximum γ-ray yield in NAA. The increase in gamma ray flux distribution in the medium of water, due to the neutron source inside the tank, has been observed by a GM detector which is due to the production of short-lived 16N on activation of 16O in water. This system can also be used for prompt γ-ray analysis.

Validation of a simple sample preparation method for multielement analysis of bovine serum.

Here we propose a single acid digestion (SAD) sample preparation method for ICP-MS analysis of animal serum samples to determine trace element contents. The method was evaluated in comparison with a commonly used procedure involving dilution of samples in an alkaline solution (AKD). In the SAD procedure, aliquots (1 mL) of bovine serum samples were treated at low temperature with a mixture of concentrated nitric acid and hydrogen peroxide. Trace elements (As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Sr, U, and Zn) were directly determined by ICP-MS analysis of diluted solutions of samples. Both methods were sufficiently sensitive to enable quantification of most trace elements, with the exception of the AKD method for Cd, Hg and Pb. The quality of the data was verified by using certified reference material. Good results were obtained for the SAD procedure and all elements, but recoveries were unacceptable with the AKD procedure for Se (recovery: 57%), Cd (154%) and Fe (139%). Strong associations (R2>0.90, P = 0.000) between the data obtained by both methods were demonstrated for the elements considered. The proposed SAD sample preparation method produced satisfactory results for determining most toxic and essential trace elements targeted in monitoring studies.

Total X-Ray Fluorescence for the Analysis of Multiple Elements in Dried Blood Spots

Dried blood spots (DBS) have been hailed as a simple way to collect, transport and store biological (blood) samples for several analytical purposes. The technique is minimally invasive which makes it a cost-effective alternative to traditional venipuncture procedures. Despite this promise, there have been challenges in measuring analyte concentrations in DBS owing to small sample volumes, concentrations, and other factors. Total Reflection X-Ray Fluorescence (TXRF) may help overcome some these barriers, and thus the aim of this research was to develop and validate a novel method to perform a multi-element analysis (copper, zinc, selenium, iron, and lead) in DBS using TXRF. A TXRF-based method for multi-element analysis was validated by analyzing DBS from different human blood standard reference materials (SRM, Institut National de Santé Publique du Québec, INSPQ; n=7) with varying and known concentrations of elements. Percent recoveries, calculated by comparing DBS to known values, and coefficients of variation were analyzed for accuracy and precision. Stability of analyses was assessed by comparing results over 16 batch runs. The method was validated by quantifying the elements of interest in capillary whole blood and DBS collected from 49 healthy individuals. The limits of quantification of Cu, Fe, Pb, Se, and Zn were 5.08, 10.7, 3.45, 3.48, and 4.50 µg/L, respectively. The precision of the method was between 3.0-15.2% for the elements of interest. Percent recoveries for Cu, Zn, Se, and Pb using an entire 25 µL DBS of SRM were 106.7± 10%, 97.9± 11.9%, 105.5± 9.2%, and 80.8± 16.40%, respectively. These results show the potential of TXRF as an alternative analytical technique to quantify multiple elements in DBS samples. The results will be further explored with ICP-MS data.

Simple method for liquid analysis by laser-induced breakdown spectroscopy (LIBS).

As a fast-developing technique for in situ multi-element analysis method, laser induced breakdown spectroscopy - LIBS is, however, developing slowly on liquid analysis due to some technical difficulties. We propose a new method, namely capillary mode, to quantify the concentrations of the elements in solution using LIBS. A Nd:YAG laser with repetition of 10 Hz were used to analyze the solution of Na2CrO4 and no any sample preparation in measurements. The experimental results show that the splashing of liquid induced by laser pulses is decreased significantly and the pollution of mirrors is avoided effectively using liquid capillary mode. The results of quantitative analysis for liquid are also improved than other method. The calibration curves of Cr and Na are well characterized by straight lines and the regression coefficient values of the linear fit are better than 0.998. The limits of detection (LODs) of Cr and Na are determined to be 28.9 mg/L and 1.0 mg/L in this work, respectively. The experimental results show that the liquid capillary mode provides a more practical and very simple approach to improve accuracy of quantitative element analysis in liquids by LIBS technique.

EDXRF as an alternative method for multielement analysis of tropical soils and sediments.

The quality assessment of tropical soils and sediments is still under discussion, with efforts being made on the part of governmental agencies to establish reference values. Energy dispersive X-ray fluorescence (EDXRF) is a potential analytical technique for quantifying diverse chemical elements in geological material without chemical treatment, primarily when it is performed at an appropriate metrological level. In this work, analytical curves were obtained by means of the analysis of geological reference materials (RMs), which allowed for the researchers to draw a comparison among the sources of analytical uncertainty. After having determined the quality assurance of the analytical procedure, the EDXRF method was applied to determine chemical elements in soils from the state of Pernambuco, Brazil. The regression coefficients of the analytical curves used to determine Al, Ca, Fe, K, Mg, Mn, Ni, Pb, Si, Sr, Ti, and Zn were higher than 0.99. The quality of the analytical procedure was demonstrated at a 95% confidence level, in which the estimated analytical uncertainties agreed with those from the RM's certificates of analysis. The analysis of diverse geological samples from Pernambuco indicated higher concentrations of Ni and Zn in sugarcane, with maximum values of 41mgkg-1 and 118mgkg-1, respectively, and agricultural areas (41mgkg-1 and 127mgkg-1, respectively). The trace element Sr was mainly enriched in urban soils with values of 400mgkg-1. According to the results, the EDXRF method was successfully implemented, providing some chemical tracers for the quality assessment of tropical soils and sediments.

Sub–1 min separation in sequential injection chromatography for determination of synthetic water-soluble dyes in pharmaceutical formulation

Sequential Injection Chromatography (SIC) evolved from fast and automated non-separation Sequential Injection Analysis (SIA) into chromatographic separation method for multi-element analysis. However, the speed of the measurement (sample throughput) is due to chromatography significantly reduced. In this paper, a sub–1min separation using medium polar cyano monolithic column (5mm×4.6mm) resulted in fast and green separation with sample throughput comparable with non-separation flow methods The separation of three synthetic water-soluble dyes (sunset yellow FCF, carmoisine and green S) was in a gradient elution mode (0.02% ammonium acetate, pH 6.7 – water) with flow rate of 3.0mLmin−1 corresponding with sample throughput of 30h−1. Spectrophotometric detection wavelengths were set to 480, 516 and 630nm and 10Hz data collection rate. The performance of the separation was described and discussed (peak capacities 3.48–7.67, peak symmetries 1.72–1.84 and resolutions 1.42–1.88). The method was represented by validation parameters: LODs of 0.15-0.35mgL−1, LOQs of 0.50–1.25mgL−1, calibration ranges 0.50-150.00mgL−1 (r>0.998) and repeatability at 10.0mgL−1 of RSD≤0.98% (n=6). The method was used for determination of the dyes in “forest berries” colored pharmaceutical cough-cold formulation. The sample matrix – pharmaceuticals and excipients were not interfering with vis determination because of no retention in the separation column and colorless nature. The results proved the concept of fast and green chromatography approach using very short medium polar monolithic column in SIC.

STUDYING REPRESENTATIVES OF WHEAT GRAIN MICROBIOTA RESISTANT TO COPPER, ZINC, MANGANESE AND IODINE SALTS

There was studied the species composition of the wheat grain microbiota, representatives of which could be potential producers of organic compounds for modern biotechnology. Twenty wheat (Triticum vulgaris) samples were tested, from microbiocenoses of which the strains of heterotrophic microorganisms resistant to toxic concentrations of copper, zinc, manganese and iodine salts were isolated and described. The contents of zinc, manganese and copper salts in a suspension of washed bacterial cells were determined using a highly sensitive multielement analysis method of inductively coupled plasma mass spectrometry (ICP-MS). Using media containing manganese, we isolated and identified Stenotrophomonas maltophilia, Bacillus cereus, Lactococcus lactis, Bacillus subtilis, Brevibacillus sp., Bacillus amyloliquefaciens. Using a medium containing 1% KJ, we isolated Vagococcus sp., Paenibacillus dendritiformis and three unidentified isolates. On a nutrient medium containing copper sulfate, one isolate of an unknown species was grown. In the presence of 1% zinc sulfate, Klebsiella pneumonia, Enterococcus faecalis, Enterococcus faecium, Ralstonia insidiosa, Stenotrophomonas maltophilia have grown that allows using them for the development of selective media. Bacteria of the genus Bacillus have been detected, which are characterized by the ability to accumulate copper compounds to a concentration of 22.3 mg/g dry biomass. The 16S rRNA gene fragment from this culture has the greatest, but incomplete (98%), homology with Bacillus sp. LY (Genbank AY787805). No data on species identity of this Bacillus strain are available in the literature studied that allows us to refer it and isolated strain Cu2 to a new species, which has not previously been described.

Novel Applications of Lanthanoides as Analytical or Diagnostic Tools in the Life Sciences by ICP-MS-based Techniques

Abstract Inductively coupled plasma mass spectrometry (ICP-MS) is a well-established analytical method for multi-elemental analysis in particular for elements at trace and ultra-trace levels. It has found acceptance in various application areas during the last decade. ICP-MS is also more and more applied for detection in the life sciences. For these applications, ICP-MS excels by a high sensitivity, which is independent of the molecular structure of the analyte, a wide linear dynamic range and by excellent multi-element capabilities. Furthermore, methods based on ICP-MS offer simple quantification concepts, for which usually (liquid) standards are applied, low matrix effects compared to other conventional bioanalytical techniques, and relative limits of detection (LODs) in the low pg g−1 range and absolute LODs down to the attomol range. In this chapter, we focus on new applications where the multi-element capability of ICP-MS is used for detection of lanthanoides or rare earth elements, which are applied as elemental stains or tags of biomolecules and in particular of antibodies.

Analysis and Speciation of Lanthanoides by ICP-MS

AbstractInductively coupled plasma mass spectrometry (ICP-MS) is based on formation of positively charged atomic ions in a high-frequency inductively coupled Argon plasma at atmospheric pressure. The ions are extracted and transferred from the plasma source into a mass analyzer operated at high vacuum via an interface equipped with a sampling and a skimmer cone. The ions are separated in the mass analyzer according to their charge to mass ratio. The ions are converted at a conversion dynode and are detected by use of a secondary electron multiplier or a Faraday cup.From an analytical point of view, ICP-MS is a well-established method for multi-elemental analysis in particular for elements at trace- and ultra-trace levels. Furthermore, methods based on ICP-MS offer simple quantification concepts, for which usually (liquid) standards are applied, low matrix effects compared to other conventional analytical techniques, and relative limits of detection (LODs) in the low pg g−1range and absolute LODs down to the attomol range. For these applications, ICP-MS excels by a high sensitivity which is independent of the molecular structure and a wide linear dynamic range. It has found acceptance in various application areas and during the last decade ICP-MS is also more and more applied for detection of rare earth elements particularly in the life sciences.Due to the fact that all molecules introduced into the high temperature of the plasma in the ion source were completely dissociated and broken down into atoms, which are subsequently ionized, all elemental species information is completely lost. However, if the different species are separated before they enter the plasma by using adequate fractionation or separation techniques, then ICP-MS can be used as a very sensitive element-specific detector. We will discuss this feature of ICP-MS in this chapter in more detail at hand of the speciation of gadolinium-containing contrast agents.

An application of PIXE technique to Proto Crustal Rocks: Geo chemical evaluation of Granulitic Charnockites of Eastern Ghats, Andhrapradesh, India

In this work, PIXE has been used for a variety of Precambrian proto crustal rocks in the form of granulitic charnockites,Eastern Ghats AP,India.In previous study of exterior part of the charnockite hill elemental analysis using electron microprobe analysis, the elements in host charnockites no Na, traces of Mn,Ca and high Ti,Cl,F (Biotite), no Mn, low Na,and high K,Cl (Hastingsite), and Cl, Fe (Apatite) were only detected, but by using PIXE technique in addition to the above twenty two trace elements are identified. PIXE is highly sensitive and non-destructive method for multi elemental analysis in a variety of Precambrian charnockite rocks down to levels of a few parts per million. The samples chosen for analysis from the central portion of a charnockite hill near Visakhapatnam airport. A big reticular mass of relict litho logical body which is compositionally and physically different from host chatnockite was observed in the central portion of the hill. These experiments are carried out using a 3MV pelletron accelerator facility at the Institute of physics, Bhubaneswar. A collimated proton beam of 2mm diameter is made to fall on to the sample, and the beam current is kept at 20na. A high resolution Si(Li) detector(160ev FWHM at 5.9kev energy) is employed in the present experiments and the Guelph PIXE (GUPIX) software package is used to analyze the spectra. The elements identified in this Precambrian charnockite rock are Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ru, Ag, Pb..From this study these rocks are early crust(proto crust) rocks. These samples are to belong to a very important geological phase and further work on petrography and REE (Rare Earth Elements in Geology)of the rock is indeed to firmly establish its exact parentage.

Empirical study of the effect of count time on the precision and accuracy of pXRF data

As a cost-effective and non-destructive method for multi-element analysis, portable X-ray fluorescence spectrometry (pXRF) has the potential for broad archeological application; however, recent applications of pXRF remain inconsistent. For example, sourcing studies using pXRF have irradiated artifacts and geologic source materials for widely varying amounts of time. In this study, we investigate the effect of count time on the precision and accuracy of pXRF data obtained for two geologic standards, as well as for obsidian, fine-grained volcanic (e.g., andesites, dacites), metamorphic, and chert specimens from the North American Great Basin. We find that the precision and reliability of pXRF data does not improve significantly at count times greater than 180s. Our analysis also indicates that count time has little bearing on the accuracy or validity of pXRF data, as expected from the mathematical relationships between count time, intensity, and concentration. Finally, we demonstrate that a well-calibrated pXRF instrument generates compositional data comparable to data obtained using other analytical methods. We offer this study as a step toward the development of a consistent and rigorous analytical protocol for archeological applications of pXRF.

Commentary: Environmental chemicals and diabetes: which ones are we missing?

Commentary: Environmental chemicals and diabetes: which ones are we missing?

Geographical characterization of Spanish PDO paprika by multivariate analysis of multielemental content

A multielemental analytical method has been proposed to determine the contents of Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Sr and Zn in paprika samples from the two Protected Designations of Origin recognized in Spain, such as Murcia and La Vera (Extremadura). The samples are mineralized by acid wet digestion using a mixture of perchloric and nitric acids and analyzed by means of inductively coupled plasma atomic emission spectroscopy. The method performance has been checked studying the absence of matrix effect, trueness, precision, linearity, limit of detection and limit of quantification. The proposed method has been applied to analyze samples of sweet, hot and hot/sweet paprika from the considered production areas. Differences between paprika samples from Murcia and Extremadura were found and pattern recognition methods, such as linear discriminant analysis, linear support vector machines, soft independent modeling of class analogy and multilayer perceptrons artificial neural networks, has been used to obtain classification models. Sweet and hot/sweet paprika types were differentiated by means of linear models and hot paprika was differentiated by using artificial neural networks. A model based on artificial neural networks is proposed to differentiate the geographical origin of paprika, with independence of the type, leading to an overall classification performance of 99%.