Extending applicability of the oxygen radical absorbance capacity (ORAC-fluorescein) assay

The ORAC-fluorescein (ORAC-FL) method recently validated using automatic liquid handling systems has now been adapted to manual handling and using a conventional fluorescence microplate reader. As calculated for Trolox, the precision of the method was <3.0, expressed as percent coefficient of variation. The accuracy of the method was <2.3, expressed as percent variation of the mean. The detection and quantification limits were those corresponding to 0.5- and 1-microM Trolox standard solutions, respectively. The method has been applied to 10 pure compounds (benzoic and cinnamic acids and aldehydes, flavonoids, and butylated hydroxyanisole), to 30 white, rose, and bottled- and oak-aged red wines, and to 7 commercial dietary antioxidant supplements. All samples exhibited a good linear response with concentration. As seen by other methodologies, the chemical structure of a compound determines its antioxidant activity (ORAC-FL value). Of particular interest were the results with oak-aged red wines from different vintages (1989-2002) that confirm influence of vintage, but not origin of the oak, in the antioxidant activity of wines from the same variety. Dietary antioxidant supplements presented a great variability (170-fold difference) in their antioxidant potency. This work proves applicability of the ORAC-FL assay in evaluating the antioxidant activity of diverse food samples.     

Countercurrent supercritical fluid extraction and fractionation of high-added-value compounds from a hexane extract of olive leaves

Countercurrent supercritical fluid extraction (CC-SFE) at a pilot scale plant was used for fractionation of high-added-value products from a raw extract of olive leaves in hexane. Compounds found in the raw extract were waxes, hydrocarbons, squalene, beta-carotene, triglycerides, alpha-tocopherol, beta-sitosterol, and alcohols. The CC-SFE extraction process was investigated according to a 2(3) full factorial experimental design using the following variables and ranges: extraction pressure, 75-200 bar; extraction temperature, 35-50 degrees C; and ethanol as modifier, 0-10%. Data were analyzed in terms of extraction yield, enrichment, recovery, and selectivity. Higher extraction yields were attained at 200 bar. For most of the compounds analyzed enrichment was attained at the same conditions, that is, 75 bar, 35 degrees C, and 10% ethanol. Hydrocarbons were usually recovered in the separators, whereas waxes and alpha-tocopherol remain in the raffinate. Selectivity data reveal that alpha-tocopherol is the most easily separable compound. The influence of the experimental factors on the recovery of all the compounds was studied by means of regression models. The best fitted model was attained for beta-sitosterol, with R2 = 99.25%.     

Organophosphorus pesticide residues in Mexican commercial pasteurized milk

A study was conducted to measure residues of 13 organophosphorus (OP) pesticides, widely used as dairy cattle ectoparasiticides or in crops used for animal feed, in homogenized and pasteurized Mexican milk samples. Four different milk brands with high distribution were collected biweekly during a 12 month period (n = 96) in supermarkets. OP pesticide residues were measured by gas chromatography with a flame photometric detector. Approximately 39.6% of the samples contained detectable levels of OP pesticide residues. Eight samples contained residues exceeding established maximum residue limits (MRL), and the OP pesticides present in these samples were dichlorvos (five samples), phorate, chlorpyrifos, and chlorfenvinphos (one sample, respectively). Average residues of 13 OP pesticides measured were below established MRLs ranging between 0.0051 and 0.0203 ppm.     

In vivo antifungal activity of the essential oil of Bupleurum gibraltarium against Plasmopara halstedii in sunflower

The antifungal activity of the essential oil of the aerial parts of Bupleurum gibraltarium was evaluated against Plasmopara halstedii. Fungus spores were inoculated in sunflower seedlings, previously treated with several essential oil solutions, and the sporulation percentage was measured after an 11-day treatment. The oil at a concentration of 5.0 mL/L clearly inhibited the fungus sporulation. The contact between fungus sporangia and essential oil was minimized, so it seems that the oil pretreatment could activate the defense response of the sunflower seedlings against the pathogen invasion. The main compounds in the oil were sabinene (31.1%), alpha-pinene (15.6%), and 2,3,4-trimethylbenzaldehyde (10.9%), among a total of 65 components identified.     

Aroma extract dilution analysis. Precision and optimal experimental design

The odor thresholds of 12 different compounds have been determined in an AEDA experiment using a panel composed of 8 individuals. Only in one case is the distribution of thresholds among judges significantly different from the log-normal. The cause of that departure from normality seems to be a cross adaptation rather than anosmia. The standard deviations (SD) range from 2(0.7) to 2(4.1), with 2(1.8) as average. If the AEDA is carried out at a dilution rate, R, and dilution R(P) (where P = 0, 1, 2.) is the last one at which a compound was detected by a judge, the flavor dilution (FD) factor that should be provided for that judge is R(P+0.5). In the case where several judges carry out the AEDA, the FD for a given compound should be the geometric mean of the FD provided by all the judges. The SD of the distribution of FDs is related to that of the distribution of odor thresholds, but is strongly influenced by the dilution rate, R, being higher with higher R values. The relationship between both SDs can be used to determine the expected precision (measured as the geometric length of the 95% confidence interval) of the result of an AEDA experiment as a function of the dilution rate, the number of judges, and the SD of the distribution of thresholds. Different simulations have shown that in most cases, a dilution rate of 10 is the best option, and that lower dilution rates are advantageous only if the analyzed solution contains compounds with a very narrow distribution of thresholds.     

Coriander essential oil composition from two genotypes grown in different environmental conditions

The objective was to study the essential oil composition of coriander fruits in plants growing in environments differing in soil conditions and weediness level. Factorial field experiments were conducted in two locations from the Rolling Pampas, Argentina, and two coriander landraces (European and Argentinean) were tested under two levels of nitrogen fertilization and weediness. Data were evaluated with uni- and multivariate techniques. The variation in the oil composition was related to the relative proportion of the constituents and not to the presence/absence of a particular component. Weather conditions in 1997 favored linalool and camphor in both landraces. Location, fertilization, and weediness also affected the chemical profile. The European landrace showed a more stable concentration of the major components than the Argentinean landrace. These results, which show the relationships between some environmental conditions and the essential oil composition, are useful in the development of innovative strategies aimed to improve oil composition and to manage crop pests.     

INCREASED CADMIUM AVAILABILITY TO CROPS ON A SEWAGE-SLUDGE AMENDED SOIL

Analysis of spatial distribution of sewage-sludge born cadmium on the experimental plot revealed positive correlation of total cadmium and organic matter. Soil pH fluctuated randomly on the field. ‘Bioavailable’ concentrations, as determined by NH₄-acetate extraction, were closely correlated to the total cadmium levels, and only negligible effects of pH and/or organic matter fluctuations were recorded. Desorption model using modified Freundlich isotherm was applied to predict risks of cadmium solubilization at different conditions. Simulations revealed that the organic matter content within the ranges found at the experimental field cannot support a proper immobilization of cadmium at pH-range observed at the field. The phenomenon was explained by ineffective care for the soil in the past.     

A rapid method for the determination of chlorine, phosphorus, and sulfur in flours of grains and legumes using wavelength dispersive x-ray flourescence spectrometry

A rapid method for the determination of chlorine, phosphorus, and sulfur in commercial flours of wheat, barley, maize, rice, field bean, and soybean by wavelength dispersive x-ray fluorescence spectrometry has been developed. The flours are strained through a 425 microns sieve, then pelletized and measured. The total analysis time for the quantitation of chlorine, phosphorus, and sulfur is less than 20 min per sample. Calibration is carried out using a standard additions method with mixed standards. The method is accurate and precise, and appears to be adequate for routine analyses.     

Removal of Copper and Cadmium Ions from Diluted Aqueous Solutions by Low Cost and Waste Material Adsorbents

The sorption of copper and cadmium ions using activated carbon,kaolin, bentonite, diatomite and waste materials such as compost,cellulose pulp waste and anaerobic sludge as sorbents is reported. Equilibrium isotherms were obtained for the adsorption of these metals in single and binary solutions. Bentonite presented the highest adsorption capacities for both copper and cadmium. A competitive uptake was observed when both metals are present; copper being preferentially adsorbed by all materials with theexception of anaerobic sludge. Equilibrium data were fitted toLangmuir and Freundlich models, with satisfactory results for most of the adsorbent-metal systems studied.Of all the adsorbents studied, bentonite and compost presentedthe highest removal efficiencies, reaching 99% for copper whencadmium is also present, for initial solution concentrations ofup to 100 mg L^-1. Anaerobic sludge has a greater preferencefor cadmium, even in the presence of copper, with removal efficiencies of 98% for similar concentrations to those mentioned above.     

Speciation of Selected Minor and Major Elements in Oil Ash I. Operationally Defined Chemical Associations and Aqueous Speciation

This study is focused on the speciation of selected elements in oil ash. Our efforts were directed primarily to obtain information on the various forms of vanadium, chromium and nickel. One sample was characterized via its total composition and via its capacity for releasing various elements. The latter was estimated by hot water and nitric acid extractios. A rapid cold water extraction technique has been developed and utilized for sample preparation prior to aqueous speciation by high pressure ion chromatography (HPIC). Results of the HPIC measurements, in agreement with electron spin resonance (ESR) investigations performed on the solid sample, indicate that 38% of the vanadium is present as VOSO₄, 58% of the chromium is Cr₂(SO₄)₃ and 30% of the nickel is NiSO₄. The pH and the redox potential values of the cold water extract support the existence of these forms. Results of a generic study with successive fractionation extractions show the probable existence of oxides, associations with organic matter and aluminosilicate minerals.