Determination of biphenyl residues in citrus fruit by derivative infrared spectrophotometry

A method for determination of biphenyl residues in whole citrus fruit is described. The mascerated fruit was distilled in an acid medium, the distillate was extracted with cyclohexane, and biphenyl was determined in the extract using various measures obtained by first and second derivative infrared (IR) spectrophotometry. Calculations were performed by PE680 and SNGLE programs on data obtained using a Perkin-Elmer Model 3600 data station. The relative precision of the determinations at 70 ppm was 1.8 to 2.0%; the detection limit was 5 ppm in all measurements, and recovery of spiking concentrations of 20 to 80 ppm ranged from 90.2 +/- 5.5% (for the amplitude of the 739 cm-1 peak of the first derivative) to 97.5 +/- 2.0% (for the trough-to-peak difference from the 737 cm-1 minimum to the 743 cm-1 maximum of the second derivative.     

Simplified micro perchlorination method for polychlorinated biphenyls in biological samples.

Simplified methodology is presented for the micro determination of polychlorinated biphenyls (PCBs) in biological samples, by conversion to the decachlorobiphenyl (DCB) derivative. Beef adipose tissue and human milk extracts were fortified with PCB standards at 0.1--5.0 ppm, and perchlorinated with antimony pentachloride (SbCl5). Several Aroclors representing various degrees of chlorine content were investigated to assess the efficiency of conversion to DCB. Samples were cleaned up on a Florisil mini column and the PCBs were quantitated by electron capture GLC. Several chlorinated pesticides which were subjected to the perchlorination procedure did not interfere. As little as 0.1 ppm PCBs in 500 mg tissue extract can be recovered at 79-99%. The background DCB content of several brands of SbCl5 was determined. The levels of PCBs in human milk obtained by the perchlorination technique are compared with data acquired by electron capture gas-liquid chromatography in which the individual chlorobiphenyls in the sample are measured.     

Levels of 3,3',4,4'-tetrachloroazobenzene in diuron and linuron herbicide formulations

Levels of 3,3',4,4'-tetrachloroazobenzene (TCAB) were determined by capillary gas chromatography (GC) with electron-capture detection (ECD) in 25 samples of diuron and linuron formulations obtained from the Canadian market. Acidic aqueous methanol was used to retain urea herbicide and the neutral TCAB was allowed to partition into hexane. Silica gel was used for cleanup of the hexane extract, followed by GC/ECD determination. Recovery data obtained at 4 different spiking levels (i.e., 0.3, 0.1, 1.0, and 5.0 ppm) in linuron averaged 93, 86, 85, and 97%, respectively. For diuron, spiking was done at 0.5, 1.0, and 5.0 ppm levels and the corresponding average percent recoveries were 95, 101, and 104. The TCAB contamination level observed in diuron on a 100% active ingredient basis ranged from 0.15 to 3.38 ppm, whereas in linuron, it varied from 0.91 to 10.28 ppm.     

Automatic method for the determination of Folin-Ciocalteu reducing capacity in food products

In the present work, an automatic flow procedure based on multi-syringe flow injection analysis was developed for the assessment of Folin-Ciocalteu reagent (FCR) reducing capacity in several types of food products using gallic acid as the standard. Different strategies for mixing of sample and reagent were tested (continuous flow of FCR, merging zones, and intercalated zones approaches); lower reagent consumption and higher determination throughput were attained for the merging zones approach (100 microL of sample+100 microL of FCR). The application of the proposed method to compounds with known antioxidant activity (both phenolic and nonphenolic) and to samples (wines, beers, teas, soft drinks, and fruit juices) provided results similar to those obtained by the conventional batch method. The detection limit was 0.6 mg L-1, and the determination frequency was about 12 h-1. Good repeatability was attained (RSD<1.3%, n=10).     

Potentiometric flow injection determination of glycerol in distilled spirits.

A single-line flow injection system including a tubular periodate-selective electrode without inner reference solution is proposed for glycerol determination in distilled spirits, based on oxidation of this polyol by periodate. Interferences due to 5.0 mg L(-1) Cu, 5000 mg L(-1) sucrose, and 3000 mg L(-1) fructose plus glucose were investigated. The procedure is characterized by a linear response for 20-500 mg L(-1) glycerol (r > 0.9999, n = 7), a relative standard deviation of results of <0.03, and an analytical throughput of 30 determinations per hour. Accuracy was assessed by applying the procedure to distilled spirits of sugarcane and grape already analyzed by HPLC; in addition, recoveries within 96 and 120% were obtained.     

Determination of sulfite in food by flow injection analysis

A method is described for the determination of sulfite levels in food products by flow injection analysis (FIA). The method is based on the decolorization of malachite green by SO2, which is isolated from the flowing sample stream by means of a gas diffusion cell. The FIA method has a detection limit in food sample extracts of 0.1 ppm SO2 (3 times peak height of blank), which corresponds to 1-10 ppm SO2 in a food product, depending on the extraction procedure used. At the 5 ppm SO2 level in a food extract, the precision of replicate injections is +/- 1-2%. The method was tested on a variety of both sulfite-treated and untreated food products and the results compared favorably with those obtained by the Monier-Williams, colorimetric (pararosaniline), and enzymatic (sulfite oxidase) methods. The average differences from the FIA results were 19, 11, and 12%, respectively, for those samples (n = 12) above 50 ppm SO2. At lower levels the results were somewhat more erratic due to inaccuracies of the various methods at low concentrations.     

Gas chromatographic-mass spectrometric method for the analysis of dimethomorph fungicide in dried hops

An analytical method for the determination of dimethomorph [(E,Z)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine] residues in dried hops was developed utilizing liquid-liquid partitioning, automated gel permeation chromatography (GPC), Florisil and aminopropyl solid phase extraction (SPE) column cleanups, and gas chromatography (GC) with mass selective detection (MSD). Method validation recoveries from dried hops ranged from 79 to 103% over four levels of fortification (0.1, 1.0, 5.0, and 20 ppm). Control and dimethomorph-treated hop samples collected from three field sites had residue levels of <0.10 and 4.06-17.32 ppm, respectively. The method was validated to the limit of quantitation at 0.10 ppm. The limit of detection for this method was 0.045 ppm.     

Determination of phenol in honey by liquid chromatography with amperometric detection

A sensitive, selective analytical method has been developed for determination of phenol in honey by liquid chromotography (LC) with amperometric detection (AMD). Phenol is extracted with benzene from the distillate of honey. The benzene extract is washed with 1% sodium bicarbonate solution and then reextracted with 0.1N sodium hydroxide followed by cleanup on a C18 cartridge. Phenol is determined by reverse-phase LC with amperometric detection. An Inertsil ODS column (150 X 4.6 mm, 5 microns) is used in the determination. The mobile phase is a mixture (20 + 80 v/v) of acetonitrile and 0.01M sodium dihydrogen phosphate containing 2mM ethylenediaminetetraacetic acid, disodium salt (EDTA) with the pH adjusted to 5.0. The flow rate is 1 mL/min under ambient conditions. The applied potential of the AMD using a glassy carbon electrode is 0.7 V vs an Ag/AgCl reference electrode. Average recoveries of phenol added to honey were 79.8% at 0.01 ppm spiking level, 90.4% at 0.1 ppm, and 91.0% at 1.0 ppm. Repeatabilities were 3.4, 1.3, and 1.8%, respectively. The detection limit of phenol in honey was 0.002 ppm. For analysis of 112 commercial honey samples, the range and average values of 32 detected samples were 0.05-5.88 ppm and 0.71 ppm, respectively.     

Direct determination of lead in evaporated milk and apple juice by anodic stripping voltammetry: collaborative study

A method for the direct determination of lead in evaporated milk and in fruit juice with no prior sample digestion was successfully collaborated by 13 laboratories. The anodic stripping voltammetric (ASV) method studied consisted of adding 0.2 mL aliquots of evaporated milk or 0.3 mL aliquots of fruit juice to 2.9 mL of a dechelating reagent, Metexchange. The reagent-sample mixture is then analyzed for lead by ASV with no further sample preparation. Each collaborator received 24 samples, 2 each at 5 different levels (0.07-0.70 ppm for spiked evaporated milk and 0.09-0.87 ppm for spiked apple juice) along with duplicate practice samples of labeled lead content at each of 2 levels for each sample type. All unknowns were coded with random numbers. Approximately 69% of the reporting laboratories had never analyzed either evaporated milk or fruit juice for lead. Average time between receipt of samples and reporting of results was 1.6 days for all laboratories. The pooled variations between duplicate determinations for apple juice and evaporated milk were 0.00059 and 0.00043, respectively. The method was adopted official first action for both fruit juice and evaporated milk.     

Gas-liquid chromatographic determination of dehydroacetic acid in squash and wine

A gas-liquid chromatographic procedure has been developed for the determination of the preservative dehydroacetic acid (DHA) in frozen cut squash and white wine. The cleanup procedure uses the acidic character of DHA to enhance separation from interfering substances. Recoveries were 93-104% from squash fortified at 30, 65, and 130 ppm and 96-99% from wine fortified at 50, 100, and 200 ppm. The method can be used to establish that the amount of DHA used in squash does not exceed the permissible level of 65 ppm.     

Dummy molecularly imprinted solid-phase extraction for selective determination of five phthalate esters in plastic bottled functional beverages

In this paper, a highly selective sample cleanup procedure combing dummy molecular imprinting and solid-phase extraction (DMI-SPE) was developed for the simultaneous isolation and determination of five phthalate esters in plastic bottled beverages. The new imprinted microspheres were synthesized via precipitation polymerization using diisononyl phthalate as a dummy template that showed high selectivity and affinity to the five kinds of phthalate esters and were successfully applied as selective sorbents of DMI-SPE for the simultaneous determination of the phthalate esters from plastic bottled beverages. Good linearity was obtained in a range of 5.0-750.0 μg/L, and the average recoveries of the five phthalate esters at three spiked levels ranged from 84.3 to 96.2% with the relative standard deviations less than 5.49%. The developed extraction protocol eliminated the effect of template leakage on quantitative analysis and could be applied for the determination of phthalate esters in complicated functional beverages products.     

Method development and fate determination of pesticide-treated hops and their subsequent usage in the production of beer

The fate of residues of seven agrochemicals (chlorfenapyr, quinoxyfen, tebuconazole, fenarimol, pyridaben, and E- and Z-dimethomorph) from the treatment on hops to the brewing of beer was studied. First, a multi-residue analytical method was developed for the determination of pesticide residues in spent hops, trub, wort, and beer. Each matrix was validated over at least two levels of fortification, for all seven compounds, in the ranges 0.05-5.0, 0.001-1.0, 0.001-0.05, and 0.0005-1.0 ppm for spent hops, trub, wort, and beer, respectively. Recoveries ranged from 73 to 136%. Second, the matrixes prepared from hops, which were treated under commercial practices with each compound, were analyzed using the method developed. The use of treated hops resulted in the carryover of 0.001 ppm of tebuconazole, 0.008 Z-dimethomorph, and 0.005 ppm of E-dimethomorph into the wort. The bulk of the remaining residues of all seven compounds was found on the spent hops. Following fermentation, all compounds were found in levels less than 0.0005 ppm in beer, except Z- (0.006 ppm) and E-dimethomorph (0.004 ppm). Third, when all seven pesticides were spiked prior to the pitching of yeast into clean wort, most of the nonpolar compounds (chlorfenapyr, quinoxyfen, and pyridaben) partitioned into the organic material (trub) which settled to the bottom, while the more polar compounds (fenarimol, tebuconazole, and E- and Z-dimethomorph) were generally distributed evenly between the beer and the trub.     

Determination of organophosphorus pesticides in fruit juices by matrix solid-phase dispersion and gas chromatography

A rapid multiresidue method was developed for the determination of nine organophosphorus pesticides in fruit juices. The analytical procedure is based on the matrix solid-phase dispersion (MSPD) of juice samples on Florisil in small glass columns and subsequent extraction with ethyl acetate assisted by sonication. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The NPD response for all pesticides was linear in the concentration range studied with determination coefficients >0.999. Average recoveries obtained for all of the pesticides in the different juices and fortification levels were >70% with relative standard deviations of <11%. The detection limits ranged from 0.1 to 0.6 microg/kg. The identity of the pesticides was confirmed by gas chromatography with mass spectrometric detection using selected ion monitoring. The proposed MSPD method was applied to determine pesticide residue levels in fruit juices sold in Spanish supermarkets. At least one pesticide was found in most of the samples, although the levels detected were very low, far from the maximum residue levels established for raw fruit.     

FTIR approaches for diuron determination in commercial pesticide formulations

Two strategies have been developed for Diuron determination by FTIR spectrometry, an off-line extraction and stopped-flow determination and a fully mechanized procedure, based on the on-line extraction of Diuron and FIA-FTIR measurement of the extracts. The aforementioned procedures have been compared with a reference chromatographic method. The off-line FTIR spectra were obtained at a nominal resolution of 4 cm(-1) from 4000 to 900 cm(-1) by accumulating 25 scans. Diuron was determined using peak height measurements at 1582 cm(-1) corrected using a baseline defined between 1562 and 1614 cm(-1). The waste generation of the off-line procedure was 3.4 mL chloroform for each sample, and the method provided a LOD of 40 microg g(-1), corresponding to 0.8% (w/w) Diuron in the original sample. The fully mechanized FIA method provided a LOD of 35 microg g(-1), which corresponds to 0.7% (w/w) in the solid sample and a maximum sampling frequency of the whole procedure of 30 h(-1), with a waste generation of 9.3 mL per sample, taking into account the volume of CHCl(3) required for sample dissolution and that need as a carrier. All those methods consume less organic solvent than a HPLC method, which involves the use of 39 mL of acetonitrile per sample and a sampling frequency of 12 h(-1).     

Preparation and promotion of fruit growth in kiwifruit of fluorinated N-phenyl-N'-1,2,3-thiadiazol-5-yl ureas

Seventeen phenyl-fluorinated analogues of thidiazuron [N-phenyl-N'-(1,2,3-thiadiazol-5-yl)urea, TDZ] have been prepared and characterized. The effects of each fluorinated urea on growth and quality of kiwifruits (Actinidia deliciosa) were evaluated by comparison with untreated (control) and TDZ-treated fruits. The results obtained showed a clear dependence of the growth-promoting activity of these fluorinated ureas on the pattern and degree of fluorine substitution in the phenyl ring. The most effective for promoting fruit growth was N-(2,3,5,6-tetrafluorophenyl)-N'-(1',2',3'-thiadiazol-5'-yl)urea at 25 ppm (at harvest, treated fruits were 58% heavier than untreated ones) followed by N-(3,5-difluorophenyl)-N'-(1',2',3'-thiadiazol-5'-yl)urea at 10 ppm (50%). Comparatively, TDZ-treated fruits were 31% (10 ppm) and 38% (25 ppm) heavier than untreated ones. The results also indicate that the effects of the more active phenyl-fluorinated ureas on some standard quality parameters of fruits, for example, percent of fruit dry matter content, soluble solids contents, total titratable acids, shape, and internal structure, are similar to those of TDZ. Quantitative structure-activity relationships have been derived for the fruit growth promoting activity of the phenyl-fluorinated analogues of TDZ.     

Flow injection chemiluminescence determination of sudan I in hot chilli sauce

A chemiluminescence method based on the luminol-H2O2 system with flow injection technology was proposed for the determination of sudan I in hot chilli sauce. It was found that sudan I could enhance chemiluminescence intensity generated from the luminol-H2O2 system. The increment of chemiluminescence intensity was proportional to the concentration of sudan I, giving a calibration graph linear over the concentration from 10 pg mL-1 to 7 ng mL-1 (R 2 = 0.9980) with the detection limit of 3 pg mL-1 (3sigma) and the quantification limit of 7.5 pg mL-1. At a flow rate of 2.0 mL min-1, one analysis cycle, including sampling and washing, could be accomplished in 60 s with a relative standard deviation of <5.0%. The method has been applied successfully to the determination of sudan I in Pixian douban, Golden Mark guilin chilli sauce, and Golden Mark satay sauce, and the recovery was 90.6-110.0%.     

Determination of methylene chloride, ethylene dichloride, and trichloroethylene as solvent residues in spice oleoresins, using vacuum distillation and electron capture gas chromatography.

A quantitative gas chromatographic (GC) method is described for the determination of residual methylene chloride, ethylene dichloride, and trichloroethylene in spice oleoresins. The proposed method involves vacuum distillation in a closed system with toluene as a carrier solvent. Quantitation by electron capture GC on Porapak Q is facilitated by water extraction and by the addition of trans-1,2-dichloroethylene as an internal standard. Recoveries from oleoresins spiked at 30, 15, and 6 ppm ranged from 93 to 102%. To assess the possibility of interference from spice volatiles, the procedure was applied to 17 different spice oleoresins from 3 different manufacturers. No interferences were found, but methylene chloride levels up to 83 ppm and ethylene dichloride levels up to 23 ppm were detected. Trichloroethylene was not detected in any of the oleoresins.     

Rapid analysis of cholesterol-elevating compounds in coffee brews by off-line high-performance liquid chromatography/high-resolution gas chromatography

A new method is proposed to analyze the cholesterol-elevating cafestol and kahweol which allows their rapid and reliable determination in different coffee brews. The method involves the preseparation of the sample by high-performance liquid chromatography, the collection of the selected fraction, and its subsequent analysis by high-resolution gas chromatography using a programmed temperature vaporizer operated in the split mode as sampling system. Under the experimental conditions investigated, recoveries as high as 87% (cafestol) and 94% (kahweol) were achieved while detection limits equal to 0.06 and 0.04 ppm for cafestol and kahweol, respectively, were obtained. Examples are given comparing levels of cafestol and kahweol resulting from the same ground roasted coffee by different brewing methods, which show the lowest values for brews prepared from coffee bags.     

Effect of Zinc and Aluminum Ions in Breadmaking

Zinc and aluminum ions as chloride or sulfate salts at 50–500 ppm metal ion (flour basis) had no detrimental effect on fermentation of yeastleavened dough. Increased mixing times (≈10–50%) due to addition of aqueous solutions of zinc (250–500 ppm) or aluminum (150–250 ppm) ions to a bread formula was overcome by withholding salt until the final mixing stage. Breads made from commercial flours (12.5% protein) containing zinc (250–500 ppm) or aluminum (150–250 ppm) ions and no oxidant had improved loaf volume and crumb grain when compared with control bread, and no off-taste. Additionally, breads with added zinc or aluminum had better crumb grains and slower firming rates when compared with breads containing optimum l -ascorbic acid (50 ppm) or potassium bromate (20 ppm). Breads made from commercial flours (11.1% protein) and three laboratory flours (11.4–13.6% protein) containing zinc (250 ppm) or aluminum (150 ppm) ions also had improved loaf volumes and crumb grains. Zinc or aluminum ions in combination with l -ascorbic acid, but not potassium bromate, had a detrimental effect on bread quality. Scanning electron microscopy of freeze-dried bread doughs revealed that zinc and aluminum ions enhanced the film-coating property of gluten. One serving (one slice, 28 g) of bread made with 250 ppm zinc ion would provide 25% of the adult recommended dietary allowance of zinc.     

Postharvest treatments for the reduction of mancozeb in fresh apples.

The objective of this study was to determine the effectiveness of chlorine, chlorine dioxide, ozone, and hydrogen peroxyacetic acid (HPA) treatments on the degradation of mancozeb and ethylenethiourea (ETU) in apples. This study was based on model experiments at neutral pH and temperature. Fresh apples were treated with two different levels of mancozeb (1 and 10 microg/mL). Several of the treatments were effective in reducing or removing mancozeb and ETU residues on spiked apples. Mancozeb residues decreased 56-99% with chlorine and 36-87% with chlorine dioxide treatments. ETU was completely degraded by 500 ppm of calcium hypochlorite and 10 ppm of chlorine dioxide at a 1 ppm spike level. However, at a 10 ppm spike level, the effectiveness of ETU degradation was lower than observed at 1 ppm level. Mancozeb residues decreased 56-97% with ozone treatment. At 1 and 3 ppm of ozone, no ETU residue was detected at 1 ppm of spiked mancozeb after both 3 and 30 min. HPA was also effective in degrading the mancozeb residues, with 44-99% reduction depending on treatment time and HPA concentrations. ETU was completely degraded at 500 ppm of HPA after 30 min of reaction time. These treatments indicated good potential for the removal of pesticide residues on fruit and in processed products.