Determination of antioxidant capacities of vegetable oils by ferric-ion spectrophotometric methods

Two ferric-ion-based total antioxidant capacity methods: 1,10-phenanthroline (Phen) and ferric reducing antioxidant power (FRAP) were used for determination of antioxidant capacities (AC) of the acetonic and methanolic extracts of vegetable oils. The obtained mean Phen and FRAP values for acetonic extracts of olive oils, rapeseed, rice and four sunflower oils (39.3–336.5 and 39.5–339.6 μmol Fe/100 g) were higher than for methanolic extracts (22.8–307.3 and 23.5–300.1 μmol Fe/100 g). However, antioxidant capacities of methanolic extracts of corn oil, blended oils and two sunflower oils with garden green flowers (56.5–312.9 and 53.9–306.5 μmol Fe/100 g for Phen and FRAP methods, respectively) were higher than for acetonic extracts of these oils (54.2–249.2 and 52.9–244.7 μmol Fe/100 g for Phen and FRAP methods, respectively). There is a linear and significant correlation between these two analytical methods (r = 0.9989 and 0.9986 for acetonic and methanolic extracts). Also, total phenolic compounds (TPC) in the studied oils correlated with their antioxidant capacities determined by Phen and FRAP methods (r = 0.9012, 0.7818 and 0.8947, 0.7830 for acetonic and methanolic extracts, respectively). The comparable precision (R.S.D. = 0.8–4.6%, 0.9–4.9% and 0.7–4.0%, 0.6–4.0% for acetonic and methanolic extracts, respectively) and sensitivity ( = 1.27 × 10⁴, 1.11 × 10⁴ and 2.62 × 10⁴ dm³ mol⁻¹ cm⁻¹) for the proposed Phen and the modified FRAP methods, demonstrate the benefit of the Phen method in the routine analysis of antioxidant capacities of vegetable oils.     

Variable alignment of high resolution data by cluster analysis

High resolution time-of-flight secondary ion mass spectrometry (HR TOF-SIMS) is a powerful surface analytical method. For complex samples, this technique may yield intricate spectra that are difficult to interpret visually. Chemometric methods are useful for data analysis. However, these methods require that spectra are represented in a matrix format. Variances in mass measurements caused by calibration or instrumental effects may present difficulties in properly aligning mass spectral peaks into the correct columns of the data matrix. Cluster analysis of resolution elements is proposed as an alternative approach to construct the data matrix. An automated method for optimizing the data alignment is presented and evaluated for standard steel samples.     

Investigation of heavy-metal uptake by vegetables growing in contaminated soils using the modified BCR sequential extraction method

The heavy metal (Cu, Fe, Co, Ni, Cd, Cr, Pb, Zn, and Mn) concentrations in soils and in vegetable samples, i.e. lettuce (Lactuca sativa L.), parsley (Petroselinum crispum), dill (Anethum graveolens), and onion (Allium cepa L.), taken from three urban vegetable gardens in Kayseri, Turkey, were determined by FAAS. The modified three-step sequential extraction procedure proposed by the European Bureau of References (BCR), now the Standards, Measurements and Testing Programme, was used in order to evaluate trace elements mobility in soil samples, and heavy-metal uptake by vegetables. Three operationally defined fractions were isolated using the BCR procedure: acid extractable (i.e. bound to carbonates), reducible (bound to Fe/Mn oxides), and oxidizable (bound to organic matter and sulphides). The vegetable samples were prepared to analysis using the wet-ashing procedure. To estimate the accuracy of the method used in analysis of the vegetable samples, the standard reference material (NIST SRM 1573a, Tomato leaves) was used. The results of recovery for all the elements were relatively satisfactory (87.7–108%). For the soil samples, the recovery values were calculated by proportioning the sum of the steps of the BCR procedure to those of the pseudototal digestion (i.e. aqua regia). In soils, the mobility of heavy metals followed the order Mn>Cd>Cu>Pb>Zn>Cr>Ni>Co>Fe. The relationship between the vegetable–metal and soil–extractable metal concentrations was examined in order to evaluate the bioavailability of metals, and the positive correlation, especially for the first (i.e. water, acid-soluble and exchangeable fraction) and for the third (i.e. oxidizable fraction) extraction steps, was obtained.     

Application of multivariate methods to scalp hair metal data to distinguish between drug-free subjects and drug abusers

Human scalp hair samples of drug-free subjects and drug abusers (heroin and cocaine-heroin abusers) were analysed for trace metals by flame atomic absorption spectrometry (FAAS), flame atomic emission spectrometry (FAES) and electrothermal atomic absorption spectrometry (ETAAS). The classification of drug-free subjects and drug abuses groups with four multivariate methods using the metal contents in hair samples as discriminant variables has been discussed. Principal component analysis (PCA), cluster analysis (CA), linear discriminant analysis (LDA) and soft independent modelling of class analogy (SIMCA) allow distinguishing the two groups correctly. However, predictions by SIMCA are less satisfactory. Thirteen elements (Ag, Al, Ca, Cd, Cr, Cu, K, Mg, Mn, Na, Ni, Pb, and Zn) were determined by FAAS/FAES/ETAAS in 53 hair samples (16 samples of drug-free people and 37 samples of drug abusers). Human hair samples were prepared as aqueous slurries as sample pre-treatment and they were analysed using the slurry sampling technique. The half-range central value transformation was novelty used as data pre-treatment to homogenise the data. Grouping in the samples (drug-free people and drug abusers) were observed by using PCA and CA (squared Euclidean distance between objects and Ward method as clustering procedure). The application of LDA gave a correct recognition assignation percentage of 91.7 and 100.0% for the drug-free people and drug abusers, respectively, at a significance of 5%, while SIMCA offered recognition percentages of 83.3 and 91.3% for drug-free people and drug abusers, respectively, also at 5%. Finally, some studies were developed to classify heroin abusers and polidrug abusers (cocaine-heroin abusers) by the cited multivariate statistical methods. Recognition percentages of 90.9 and 100.0% were reached for heroin abusers and polidrug abusers groups, respectively, after LDA, while these percentages decreased to percentages lower than 90.0% when SIMCA was applied.     

Multivariate analysis of chromatographic retention data and lipophilicity of phenylacetamide derivatives

One of the most important physicochemical parameters of a molecule that determines its bioactivity is its lipophilicity. Cluster analysis (CA), principal component analysis (PCA), and sum of ranking differences (SRD) were used to compare the lipophilic parameters of twenty phenylacetamide derivatives, obtained experimentally as chromatographic retention data in the presence of different solvents and calculated by different mathematical methods. All the applied methods of multivariate analysis gave approximately similar grouping of the studied lipophilic parameters. In the attempt to group the investigated compounds in respect of their lipophilicity, the obtained results appeared to be dependent on the applied chemometric method. The CA and PCA, grouped the compounds on the basis of the nature of the substituents R₁ and R₂, indicating that they determine to a great extent the lipophilicity of the investigated molecules. Unlike them, the SRD method could not be used to group the studied compounds on the basis of their lipophilic character.     

Sample preparation and data interpretation procedures for the examination of xenobiotic compounds in skin by indirect imaging MALDI-MS

Aspects of the indirect examination of xenobiotic distribution on the surface of and within skin sections by imaging matrix assisted laser desorption ionisation mass spectrometry (MALDI-MS) have been examined. A solvent assisted blotting technique previously developed for the examination of the absorption of agrochemicals into leaves has been examined for the analysis of the distribution of hydrocortisone on the surface of skin. It was found that by careful control of the extraction and blotting procedure an 80-fold sensitivity improvement could by obtained over dry blotting with only 10% lateral diffusion of the image. However, in contrast it was found that the use of a hydrophobic blotting membrane was more suitable for the examination of the transdermal absorption of the pesticide chlorpyrifos.The potential of incorporating a derivatisation step into the solvent assisted blotting procedure was investigated by blotting isocyanate treated skin onto a methanol soaked blotting membrane. This served the dual purpose of derivatising the isocyanate to a stable substituted urea derivative and extracting it from the skin. Preliminary data indicate that this approach may have some merit for field sampling for such compound and clearly derivatisation also offers the potential for sensitivity enhancements.Finally, the use of principal components analysis with an ion species specific normalisation procedure is proposed to identify regions of drug treated skin where the ion abundance of the compound of interest is low.     

涡旋提取-改进BCR法测定土壤中重金属的化学形态

土壤中重金属的化学形态更能表明其迁移性和生物毒性。传统的重金属化学形态检测方法BCR法由于其提取时间长,影响检测效率。采用涡旋提取对传统BCR法进行方法优化,对土壤中Cu、Zn、Pb、Cd、Ni、Cr等6种重金属元素化学形态进行了实验分析。研究了涡旋转速、涡旋时间以及涡旋提取的方法精密度与准确度。结果表明,当涡旋转速为2500rpm,酸可交换态涡旋10min,可还原态涡旋10min,可氧化态涡旋5min时,涡旋提取效果良好。采用土壤标准物质对方法的适用性进行了验证,6种元素的检出限在0.4?32μg/kg,测定值均在标准值范围内,相对标准偏差在0.3%?5.5%之间。涡旋提取-改进BCR法分析速度快,灵敏度高,能满足同时测定土壤中多种金属元素化学形态的检测要求。     

Some sources of variability in application of the three-stage sequential extraction procedure recommended by BCR to industrially-contaminated soil

Copper, lead, manganese and zinc have been determined in extracts of industrially-contaminated soil to investigate possible sources of variability in the three-stage sequential extraction procedure recommended by BCR. Analysis was performed by flame or electrothermal atomic absorption spectrometry, using reagent matched, multi-element standard solutions. Interferences were assessed by use of a single-point standard addition. Although the distribution of contaminants in the soil was expected to be heterogeneous, little difference in precision was found when replicate samples ranging in mass from 1–5 g were extracted, provided the extractant:soil ratio was kept constant. Significant differences in operational speciation were, however, obtained when the procedure was carried out independently by three different analysts. This may be due to the critical effect of pH in Step 2. Reproducibility was higher for air-dried than for field-moist soils, but larger amount of metals were extracted, suggesting alterations in speciation occurred during drying.     

The utilization of modified BCR three-step sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in soil reference materials of different origins

A modified three-step sequential extraction procedure for the fractionation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) has been applied to the Slovak reference materials of soils (soil orthic luvisols, soil rendzina and soil eutric cambisol), which represent pedologically different types of soils in Slovakia. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). The fractions extracted were: exchangeable (extraction step 1), reducible-iron/manganese oxides (extraction step 2), oxidizable-organic matter and sulfides (extraction step 3). The sum of the element contents in the three fractions plus aqua-regia extractable content of the residue was compared to the aqua-regia extractable content of the elements in the origin soils. The accuracy obtained by comparing the determined contents of the elements with certified values, using BCR CRM 701, certified for the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in sediment following a modified BCR-three step sequential extraction procedure, was found to be satisfactory.     

Evaluation of the lipophilicity of selected sunscreens—A chemometric analysis of thin‐layer chromatographic retention data

The lipophilicities of 22 selected sunscreens, preservatives, and vitamins used in topical skin products were measured by thin‐layer chromatography. Lipophilicity was calculated in silico from the sunscreen molecular structures and compared to the experimental octanol/water partition coefficients found in the literature. The retention of the compounds was investigated on an RP‐18 stationary phase with mobile phases consisting of water and one of six organic modifiers (dioxane, tetrahydrofuran, acetone, acetonitrile, methanol, and dimethylformamide) at different concentrations. The theoretical lipophilicities were calculated by several computational algorithms and the results of these calculations were compared using cluster analysis. The results showed that two out of the six investigated organic modifiers (dioxane and acetone) may be used to estimate the octanol/water partition coefficients of highly lipophilic compounds having lipophilicities that cannot be measured directly by the shake‐flask method.     

Methods of multivariate data analysis applied to the investigation of fen soils

Fen soils from two sites of the Rhin-Havel-Luch, a peatland in the north-east of Germany, have been investigated. The samples have been collected in two horizons, representing different degrees of degradation and mineralisation of peat. Gravimetric measurements, energy dispersive X-ray fluorescence (EDXRF), elemental analysis, and ¹H low resolution nuclear magnetic resonance (LR-NMR) of the fen soil samples have been performed. By multivariate analysis of all the experimental data, especially by the principal component analysis (PCA) and by the cluster analysis, respectively, it was possible to classify the fen soils, to identify their characteristic properties, to detect temporal and local variations, and to prove representative field sampling. Furthermore, the correlation between variables of the applied analytical methods could be interpreted in context to the composition of fen soils and mutual influences of their properties.     

Coffee aroma—Statistical analysis of compositional data

Solid-phase microextraction in headspace mode coupled with gas chromatography-mass spectrometry was applied to the determination of volatile compounds in 30 commercially available coffee samples. In order to differentiate and characterize Arabica and Robusta coffee, six major volatile compounds (acetic acid, 2-methylpyrazine, furfural, 2-furfuryl alcohol, 2,6-dimethylpyrazine, 5-methylfurfural) were chosen as the most relevant markers. Cluster analysis and principal component analysis (PCA) were applied to the raw chromatographic data and data processed by centred logratio transformation.     

Classification of gasoline by octane number and light gas condensate fractions by origin with using dielectric or gas-chromatographic data and chemometrics tools

The approach for classification of gasoline by octane number and light gas condensate fractions by origin with using dielectric permeability data has been proposed and compared with classification of same samples on the basis of gas-chromatographic data. The precision of dielectric permeability measurements was investigated by using ANOVA. The relative standard deviation of dielectric permeability was in the range from 0.3 to 0.5% for the range of dielectric permeability from 1.8 to 4.4. The application of exploratory chemometrics tools (cluster analysis and principal component analysis) allow to explicitly differentiate the gasoline and light gas condensate fractions into groups of samples related to specific octane number or origin. The neural networks allow to perfectly classifying the gasoline and light gas condensate fractions.     

Principal component analysis and cluster analysis for the characterisation of marbles by capillary electrophoresis

Chemical characterisation has been carried out on 25 quarry marbles collected from Marmara, Aegean and Thrace regions of Turkey. Ten elements were determined by capillary electrophoresis (CE). Principal component analysis and cluster analysis techniques were utilised to define grouping of different marble samples. These techniques showed that the analysed marbles were differentiable mainly by provenance. Experimental conditions such as pH, applied voltage and concentration of α-hydroxyisobutyric acid (HIBA) were optimised to achieve the best separation of metal ions using central composite design. The optimum pH 3.7, applied voltage 15 kV and concentration of HIBA 10 mM were found to provide the best separation for all metal ions investigated.     

An evaluation of the modified BCR sequential extraction procedure to assess the potential mobility of copper and zinc in MSW

Copper and zinc were determined in municipal solid waste (MSW) samples with different deposit ages from Tianziling landfill site. The pseudototal metal contents of the MSW samples were determined following an aqua regia digestion. Operational speciation was performed using the modified BCR sequential extraction procedure. Analyses were carried out by AAS. Agreement between most of triplicate samples was acceptable. The amount of copper and zinc extracted in the sequential procedure (i.e. Step 1, Step 2, Step 3, residual) did not generally agree well with pseudototal digestion. Various MSW samples contained significant different levels of copper and zinc, but these were with different potential migrations. For example, 49.88%-76.34% of copper existed in five MSW samples was present as oxidable fraction while ~ 40% of zinc was present as acid soluble fraction. The study illustrates the feasibility and importance of modified BCR sequential extraction procedure used as evaluation method when assessing the potential mobility of heavy metal in MSW landfill.     

Determination of molybdenum in extracts of soil and sewage sludge CRMs after fractionation by means of BCR modified sequential extraction procedure

A modified three-step sequential extraction procedure proposed by the Commission of European Communities Bureau of Reference (BCR) was applied to certified reference materials of three different soil groups (rendzina, luvisol, and cambisol) and sewage sludge of different compositions originating from a municipal water treatment plant in order to assess potential mobility and the distribution of molybdenum in the resulting fractions. In the soils examined, molybdenum was present almost entirely in the mineral lattice, the content of molybdenum in the fractions of the studied reference materials of sludges was predominant in the fraction, represents Mo bound to organic matter and sulphide.The internal check of accuracy was performed on the results of the sequential extraction by comparing of the extractable amounts of molybdenum in the sequential procedure with the results of the pseudototal digestion of original samples. The recovery ranged from 96 to 101% and the precision (RSD) in the extracts was below 10%.     

Chemometric data analysis of pollutants in wastewater—a case study

In this study, chemometric techniques such as cluster analysis (CA), discriminant analysis (DA), principal component analysis (PCA) and partial least squares (PLS) were used to analyse the wastewater dataset to identify the factors which affect the composition of sewage of domestic origin, spatial and temporal variations, similarity/dissimilarity among the wastewater characteristics of cis- and trans-drains and discriminating variables. Samples collected from 24 wastewater drains in Lucknow city and from three sites on Gomti river in the month of January/February, May, August and November during the period of 5 years (1994-1999) were characterized for 32 parameters. The multivariate techniques successfully described the similarities/dissimilarities among the sewage drains on the basis of their wastewater characteristics and sources signifying the effect of routine domestic/commercial activities in respective drainage areas. Spatial and seasonal variations in wastewater composition were also determined successfully. CA generated six groups of drains on the basis of similar wastewater characteristic. PCA provided information on seasonal influence and compositional differences in sewage generated by domestic and industrial waste dominated drains and showed that drains influenced by mixed industrial effluents have high organic pollution load. DA rendered six variables (TDS, alkalinity, F, TKN, Cd and Cr) discriminating between cis- and trans-drains. PLS-DA showed dominance of Cd, Cr, NO₃, PO₄ and F in cis-drains wastewater. The results suggest that biological-process based STPs could treat wastewater both from the cis- as well as trans-drains, however, prior removal of toxic metals will be required from the cis-drains sewage. Further, seasonal variations in wastewater composition and pollution load could be the guiding factor for determining the STPs design parameters. The information generated would be useful in selection of process type and in designing of the proposed sewage treatment plants (STPs) for safe disposal of wastewater.     

Evaluation of chemometric techniques for the identification and quantification of solvent mixtures using a thin-film metal oxide sensor array

An evaluation was made of suitable chemometric techniques that can be used in both the selection of suitable sensors for a sensor array and the subsequent identification and quantification of analytes using such a device. Data fro a thin-film tin oxide-based gas sensor were obtained for a range of analytes, both pure and in mixtures and analysed using several chemometric techniques, including principal component analysis, cluster analysis and partial least squares. It was shown that the array produced a characteristic response pattern for the analytes, and this was then used for the identification of ethyl acetate, acetone, ethanol and pentane, and the determination of ethanol in various mixtures. The chemometric techniques were not only used to identify and quantify components in the solvent mixture but also indicated which of the array elements were acting independently and the level of interaction which was occurring. The results obtained describe a chemometric and fabrication protocol for sensor array design.     

Patterns in the precision of quantitative data from multicomponent gas chromatographic or gas chromatographic-mass spectrometric analysis

The dispersion of the quantitative results in the analysis of volatile compounds from multicomponent mixtures by different fractionation techniques (solid-phase microextraction and direct thermal desorption) followed by GC or GC-MS presents nonrandom patterns related to the existence of different factors in the fractionation process or in the chromatographic separation which affect, to a different extent, the recovery of the sample components. Statistical techniques have been used to show the relative importance of these factors. The improvement in data precision achieved by using volatile compound concentration ratios is discussed.     

Thallium fractionation in polluted environmental samples using a modified BCR three-step sequential extraction procedure and its determination by electrothermal atomic absorption spectrometry

Determination of thallium in polluted environmental samples and their extracts obtained by a modified BCR three-step sequential extraction procedure was used to study thallium distribution and mobility in the monitored polluted area affected by acidification (Šobov, Central Slovakia). The results of fractionation applied to 5 soil certified reference materials and 14 environmental samples show that the vast majority of thallium occurred in the residual fraction. This means that highly toxic thallium is strongly entrapped in the parent rock materials remains immobile and its environmental toxicity is therefore reduced. The limit of detection for thallium in the studied fractions was lower than 0.050 mg kg⁻¹, the precision (RSD) of the ultratrace determination of thallium in the studied fractions was better than 17 % and the accuracy of the used method was verified by analyzing certified reference materials. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.