Multiresidue analysis of pesticides in vegetables and fruits using two-layered column with graphitized carbon and water absorbent polymer.

A high-throughput multiresidue analysis of pesticides in non-fatty vegetables and fruits was developed. The method consisted of a single extraction and a single clean-up procedure. Food samples were extracted with ethyl acetate and the mixture of extract and food dregs were poured directly into the clean-up column. The clean-up column consisted of two layers of water-absorbent polymer (upper) and graphitized carbon (lower), which were packed in a reservoir (75 ml ) of a cartridge column. The polymer removed water in the extract while the carbon performed clean-up. In a recovery test, 110 pesticides were spiked and average recoveries were more than 95% from spinach and orange. Most pesticides were recovered in the range 70-115% with RSD usually < 10% for five experiments. The residue analyses were performed by the extraction of 12 pesticides from 13 samples. The two methods resulted in similar residue levels except chlorothalonil in celery, for which the result was lower with the proposed method. The results confirmed that the proposed method could be applied to monitoring of pesticide residue in foods.

GC/MS analysis of polybrominated diphenyl ethers in fish collected from the Inland Sea of Seto, Japan.

Development of an analytical method for polybrominated diphenyl ethers (PBDEs) in fish and their concentration in Japanese marine fish were investigated. Fish homogenate was extracted with diethyl ether/hexane (1 + 3). The extract was cleaned up by automated gel permeation chromatography (GPC) and then by mini-column chromatography, which consisted of three layers of silica gel and sulfuric acid-impregnated silica gel. The PBDE fraction was concentrated and injected into a GC/MS with negative chemical ionization (NCl). Recoveries of the 15 individual PBDEs (BDE-15, 28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, and 209) each at a fortification level of 4 ng/g lipid were in the range of 88-128% and the relative standard deviations (RSD) were 0.43-7.6% (n = 4). Seven species of marine fish (conger eel, flounder, gray mullet, horse mackerel, red sea bream, sea bass, and yellowtail) were collected from the Inland Sea of Seto, and were analyzed with the developed method. Seven PBDEs (BDE-28, 47, 66, 99, 100, 153, and 154) were detected in all the samples. The most abundant PBDE congener was BDE-47 found in all the samples. Relatively high levels of PBDEs were found in the gray mullets and yellowtails.

[Drying ability of anhydrous sodium sulfate on wet organic solvents after liquid-liquid partition].

Water concentration in organic solvents after liquid-liquid partition was determined by the Karl Fischer titration method. n-Hexane and petroleum ether showed quite low levels of water, such as 0.1 mg/mL. The water concentration in wet ethyl acetate was about 20-30 mg/mL and that in diethyl ether was about 8-10 mg/mL. Anhydrous sodium sulfate absorbed about 20-25% of the water after vigorous mixing with wet ethyl acetate or diethyl ether. Wet acetonitrile extract from wet food, which contained about 60 mg/mL water after salting out with sodium chloride, was not dried at all with anhyfrous sodium sulfate treatment. Spiking n-hexane into wet ethyl acetate or wet diethyl ether was effective to exclude water. Spiking toluene into salted acetonitrile drove out water and dissolved sodium chloride. It can be concluded that the drying ability of anhydrous sodium sulfate towards wet organic solvents is poor, but it is effective in removing suspended water in solvents.

Determination of triazine herbicides in foods with liquid chromatography mass spectrometry.

Eight residual triazine herbicides and three metribuzin metabolites in foods were determined by liquid chromatography mass spectrometry (LC-MS) with an atmospheric pressure chemical ionization (APCI) interface, under both positive and negative ion modes. Herbicides were extracted with acetonitrile, and no cleanup procedure was adopted in this method. Four foods were spiked with eight herbicides and three metabolites at 0.05 ppm. The average recoveries of these herbicides usually ranged from 82 to 99% and the relative standard deviations were usually around 10%. These results suggest that LC-MS with APCI can be used to determine residues of triazine herbicides in foods.

Multiresidue analysis of pesticides in vegetables and fruits using a high capacity absorbent polymer for water.

A single extraction and a single clean-up procedure was developed for multi-residue analysis of pesticides in non-fatty vegetables and fruits. The method involves the use of a high capacity absorbent polymer for water as a drying agent in extraction from wet food samples and of a graphitized carbon column for clean-up. A homogeneously chopped food sample (20 g) and polymer (3 g) were mixed to absorb water from the sample and then 10 min later the mixture was vigorously extracted with ethyl acetate (100 ml). The extract (50 ml), separated by filtration, was loaded on a graphitized carbon column without concentration. Additional ethyl acetate (50 ml) was also eluted and both eluates were concentrated to 5 ml for analysis. The procedure for sample preparation was completed within 2 h. In a recovery test, 107 pesticides were spiked and average recoveries were more than 80% from asparagus, orange, potato and strawberry. Most pesticides were recovered in the range 70-120% with usually less than a 10% RSD for six experiments. The results indicated that a single extraction with ethyl acetate in the presence of polymer can be applied to the monitoring of pesticide residues in foods.

Determination of N-methylcarbamate pesticides in foods using an accelerated solvent extraction with a mini-column cleanup.

Residual N-methylcarbamate pesticides in food were determined by accelerated solvent extraction (ASE) and HPLC with post-column fluorescence. Pesticides were extracted with acetonitrile at 100 degrees C under 2000 psi pressure in less than 20 min. Extracts were cleaned-up with a carboxylic acid mini-column eluted with 10% or 30% acetone in hexane. Eight foods were spiked with 17 pesticides at 0.2 ppm. The average recoveries of these pesticides were 70-100% and the relative standard deviations were < 10%. These results suggested that ASE can be used to extract residues of N-methylcarbamate pesticides in foods.

Determination of organophosphorus pesticides in foods using an accelerated solvent extraction system.

Residual organophosphorus pesticides in foods were determined by accelerated solvent extraction (ASE), gel permeation chromatography and GC-FPD. Pesticides were extracted at 100 degrees C under 1500 psi pressure in less than 20 min. Wet samples were extracted after mixing with Extrelut drying agent. Four foods were spiked with 19 pesticides at 0.1 ppm or less. The average recoveries of these pesticides were 80-90% and the precision was < 10%. Both methamidophos and acephate gave 37-50% recoveries and 6-40% precision. These results suggested that ASE can be used to extract residues of organophosphorus pesticides in foods.