Comparison of analytical methods for metribuzin.

Determinations of the active ingredient in technical and formulated metribuzin were compared by gas-liquid chromatography (GLC) using various solvents, infrared (IR) spectrophotometry, and high-pressure liquid chromatography (HPLC). Ketones could not be used as a solvent for GLC analysis because of Schiff base formation. The GLC method using ethylene glycol monomethyl ether gave results about 1% higher for technical metribuzin than the other methods. GLC using methylene chloride solvent agreed with IR and HPLC results to within 0.4%. GLC using methylene chloride is the preferred method.     

Substances interfering with the gas-liquid chromatographic determination of T-2 mycotoxin.

Two substances interfering with the gas-liquid chromatographic (GLC) detection of T-2 mycotoxin were identified as 1-glyceryl-monooleate and 1-glycerylmonolinoleate. These monoglycerides are natural products formed by species of Fusarium growing on cereal grains and are also additives contained in liquid vegetable and animal fats added to the feed mixture. The monoglycerides can be removed from the analytical sample by resolution by thin layer chromatography prior to separation by GLC. Trimethylsilyl ether derivatives of the monoglycerides and T-2 toxin have almost identical retention times on 3% OV-1 columns, whereas the trifluoroacetyl and pentafluoropropionyl derivatives give baseline separation on the same column. The monoglycerides can be misidentified as the T-2 toxin in analyses involbing GLC.     

Gas-liquid chromatographic determination of p-chloroacetanilide in acetaminophen

Gas-liquid chromatography GLC) coupled with column chromatography was used to accurately determine as little as 25 ppm p-chloroacetanilide in acetaminophen. p-Chloroacetanilide was eluted from a pH 8 phosphate-buffered diatomite partition column by using purified tetrachloroethylene (acetaminophen was retained). This solution was concentrated, internal standard (docosane) was added, and p-chloroacetanilide was determined by using a 0.9 m X 2 mm glass column packed with 3% Poly A 103 on Supelcoport and a flame ionization detector with electronic integration. Standard curves were linear for 10-100 ppm p-chloroacetanilide. Various chromatographic materials were investigated for optimal retention characteristics. High pressure liquid chromatography (HPLC) was also evaluated as an alternative; however, lack of reproducibility of the HPLC column favored the GLC procedure.     

Estimation of Free Glycolipids in Wheat Flour by HPLC

The chloroform-acetone mixture (4:1, v/v) was an effective solvent for eluting the nonpolar lipid fraction, including free fatty acids, from the polar lipid (glycolipid and phospholipid) fractions from free lipids of 21 hard winter wheat flours using a solid-phase extraction system. Amounts of monogalactosyldiglycerides (MGDG) and digalactosyldiglycerides (DGDG) in the glycolipid fraction were determined by normal-phase HPLC with a gradient system using an evaporative light-scattering detector (ELSD) and a diode array detectors (DAD). Unsaturated fatty acids showed higher UV absorbances from 200 to 213 nm when compared with saturated palmitic acid. However, significant linear correlation coefficients were obtained between the peak areas measured by a DAD and GL contents determined by an ELSD, suggesting that fatty acid composition of flour GL could be fairly constant. Using an ELSD as a reference, equations for determination of MGDG or DGDG quantities were derived from the peak areas of a DAD by multivariate regression methods. Determination of MGDG and DGDG quantities was also possible using only a DAD.     

International mycotoxin check sample program: Part I. Report on laboratory performance for determination of aflatoxins B1, B2, G1, and G2 in raw peanut meal, deoiled peanut meal, and yellow corn meal

Three aflatoxin-contaminated samples (raw peanut meal, deoiled peanut meal, and yellow corn meal) were analyzed by 121 laboratories in 31 countries. Sufficient data were obtained to permit a statistical comparison of the performance of laboratories using the BF, CB, and EEC methods and those using high performance liquid chromatography (HPLC) for quantitation. No significant differences were found between means for laboratories using these 4 methods for the analysis of raw peanut meal or yellow corn meal. However, for deoiled peanut meal, means were significantly different for laboratories using the BF method compared with the CB or EEC methods for B1 and B2, and for laboratories using the CB method compared with HPLC methods for G2.     

Comparative study of methods for the extraction of eleven organophosphorus pesticide residues in rice.

Several extraction methods are compared for the simultaneous analysis of organophosphorus pesticides in unpolished rice. Four stationary phases were used for the subsequent gas-liquid chromatographic (GLC) determination of the selected pesticides. Using 3 different GLC columns, 11 pesticides were completely separated and identified. The efficiency of the cleanup and the sensitivity of the analytical method were evaluated by using powdered unpolished rice samples fortified with the pesticides and also wheat and dried bean samples. Average recoveries ranged from 74.7% for disulfoton to 97.4% for malathion in unpolished rice and from 68.1% for disulfoton to 108.3% for malathion in other crops. The method described is applicable to the analysis of selected organophosphorus pesticide residues in unpolished rice, wheat, buckwheat, and dried beans.     

Quantitation of polychlorinated biphenyl residues by electron capture gas-liquid chromatography: reference material characterization and preliminary study.

Weight per cent compositions of individual peaks of Aroclors 1016, 1242, 1248, 1254, and 1260 were determined under standard gas-liquid chromatographic (GLC) conditions. The GLC peak compositions were determined by using a Hall electrolytic conductivity detector for chlorine measurement and chemical ionization mass spectrometry with single ion monitoring for molecular weight characterization. The Aroclors used are available as reference materials for individual peak quantitation of polychlorinated biphenyl (PCB) residues by electron capture GLC. On the basis of a limited interlaboratory study and a collaborative study, the individual peak method shows improved interlaboratory precision and/or accuracy in PCB quantitation over existing methods.     

Amino acid analysis by capillary gas chromatography

Two developments have enabled major advancements in the use of capillary gas chromatography (GC), the result being its much more widespread use in investigations on a broad range of chemical and biological problems. The 2 technological developments were the introduction of fused silica capillary columns and the development of immobilized stationary phases for capillary GC columns. Because fused silica columns with immobilized stationary phases of varying polarities are offered by numerous vendors of chromatographic equipment, they have become widely used for many analytical tasks. We conducted a study to compare the effectiveness of commercially available fused silica capillary columns with the classical ion-exchange method in the separation and quantitation of amino acids. We selected the N-trifluoroacetyl (TFA) n-butyl and the N-heptafluorobutyryl (HFB) isobutyl ester derivatives for this study because of the extensive research and application of these derivatives during the past 20 years. The amino acid content of hydrolysates of 5 materials was measured: ribonuclease, beta-lactoglobulin, lysozyme, soybean meal, and a commercial poultry feed. Single 6N HCl hydrolysates of each material were prepared to minimize sample preparation differences, and 3 independent analyses of each hydrolysate were made by each of 3 techniques: the N-TFA n-butyl and N-HFB isobutyl ester methods using capillary gas chromatography and the ion-exchange chromatographic method using a Beckman 121 M amino acid analyzer. Our results clearly demonstrate that capillary GC analysis of amino acids using fused silica bonded-phase columns provides data with good precision and in general excellent agreement with ion-exchange analyses.     

Polycyclic aromatic hydrocarbon profile analysis of high-protein foods, oils, and fats by gas chromatography.

A method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) with 3-7 rings in (I) meat, poultry, fish, and yeast; and (II) oils and fats. The extraction of PAHs from group I is incomplete, and, therefore, group I samples must be dissolved homogeneously by saponification in 2N methanolic potassium hydroxide. The PAHs are concentrated by liquid-liquid extraction (methanol-water-cyclohexane, N,N - dimethylformamide - water-cyclohexane) and by column chromatography on Sephadex LH 20. The PAHs are separated by high-performance gas-liquid chromatography (GLC) with columns containing 5% OV-101 on Gas-Chrom Q and estimated by integration of the flame ionization detector signals in relation to an internal standard (3,6-dimethylphenanthrene and/or benzo(b)chrysene). The sensitivity is significantly higher than that obtained with ultraviolet spectroscopic methods. The reproducibility and margin of error were tested with meat samples fortified with 11 PAHs and with samples of sunflower oil. The method was further applied to meat, smoked fish, yeast, and unrefined sunflower oil. All samples investigated contained more than 100 PAHs (characterized by mass spectrometry) of which only the main components were determined: phenanthrene, anthracene, fluorene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene + benzo (j)fluoranthene + benzo(k) fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, dibenz(a,j)anthracene, dibenz(a,h)anthracene + indeno(1,2,3,-cd)pyrene, benzo(ghi)perylene, anthanthrene, and coronene. In contrast to other methods, the GLC profile analysis allows the recording of known and unknown PAH peaks simultaneously and also allows a compilation of all PAHs.     

Quantitative multiresidue analyses for volatile organics in water and milk, using a fused silica open-tubular wide-bore capillary column and automated headspace gas chromatography

A modified multiresidue capillary gas chromatographic (GC) procedure has been developed using automated headspace sampling and a wide-bore fused silica open-tubular (FSOT) capillary column for the determination of volatiles in water and milk. Compounds are quantitated by the method of standard additions. An IBM System 9000 computer with the CAPMC3 chromatographic applications package and a BASIC linear regression program are used for data reduction. Data are presented for solutions prepared by fortifying water and milk with volatile solvents such as acetone, methyl ethyl ketone, benzene, methylene chloride, and chloroform, which are commonly used in the manufacture of packaging materials and adhesives. The wide-bore FSOT capillary columns showed dramatically improved detection for certain compounds, compared with normal-bore capillary GC columns. Data presented for various chemicals demonstrate the improved limits of detection from the use of automated headspace gas chromatography with wide-bore capillary columns and flame ionization detection.     

Evaporative light-scattering analysis of sulforaphane in broccoli samples: Quality of broccoli products regarding sulforaphane contents

Broccoli sulforaphane has received attention as a possible anticarcinogen. Sulforaphane analysis is difficult due to the lack of a chromophore for spectrometric detection. Hence, we developed a method for determining sulforaphane by using high-performance liquid chromatography (HPLC) coupled with an evaporative light-scattering detector (ELSD). Sulforaphane was extracted from acid-hydrolyzed broccoli samples, followed by solid-phase extraction and reversed-phase HPLC. Sulforaphane was detected by ELSD and concurrently identified by electrospray ionization time-of-flight mass spectrometry. The recovery of sulforaphane from broccoli samples was above 95%. The detection limit was 0.5 mug. The present method was sensitive enough to determine sulforaphane in mature broccoli, broccoli sprouts, and commercial broccoli products. Sulforaphane concentration in broccoli sprout (1153 mg/100 g dry weight) was about 10 times higher than that of mature broccoli (44-171 mg/100 g dry weight). Therefore, the broccoli sprout is recommended as a source of sulforaphane-rich products. In contrast, we found that sulforaphane could not be detected in most of broccoli products, suggesting present commercial broccoli products having low quality.     

Identification of triacylglycerol species from high-saturated sunflower (Helianthus annuus) mutants

The triacylglycerol (TAG) composition of oils from new high-saturated sunflower lines has been studied by means of GLC. The TAG profiles have been compared with the TAG reconstruction made after lipase hydrolysis (according to the 2-random 1,3-random theory). New TAG species with asclepic (cis,Delta11-octadecenoic acid, isomer of oleic acid), araquidic, or behenic acids have been synthesized and identified in oils from mutant lines. The TAG molecular species that contain asclepic acid instead of oleic acid have a longer retention time. Because each mutant oil has a specific TAG GLC pattern, this method could be used for a more precise validation of oil type than current fatty acid methyl ester analysis. The comparison of the results obtained by GLC with the reconstruction after pancreatic lipase hydrolysis shows, in general, a good agreement between both methods. However, results shown in this paper show that this is not always the case. TAG species containing two molecules of linoleic acid show a higher presence of palmitic or stearic acid than could be expected from a random distribution. The abundance of SLL increased in proportion to the stearic acid content of the oil, and the amount of TAG species with three unsaturated fatty acids (LLL or OLL) was therefore reduced.     

Improved liquid chromatography methods for the separation and quantification of biotin in NIST standard reference material 3280: multivitamin/multielement tablets

Two independently developed liquid chromatography (LC) methods for the quantitative determination of biotin in multivitamin/multielement tablets (NIST Standard Reference Material 3280 (SRM 3280)) are described. The methods use distinctly different tablet extraction solvents (methanol vs 1.5% aqueous formic acid) and analyte detection principles (mass spectrometry (MS) versus evaporative light-scattering detection (ELSD)) to ensure quantitative reliability. The use of different extraction and detection procedures allows cross-validation of the methods and enhances confidence in the final quantitative results. Both methods yield highly comparable results for the mean level of biotin (LC/MS = 26.5 mg/kg +/- 0.3 mg/kg (n = 12); LC/ELSD = 24.7 mg/kg +/- 1.7 mg/kg (n = 12)) in SRM 3280, yet the methods differ considerably in their analytical characteristics. The isotope-dilution LC/MS method exhibits excellent linearity from 0.02 ng to 77 ng biotin on-column with a method limit of detection (LOD) and limit of quantification (LOQ) of 0.02 ng (S/N > 3) and 0.06 ng (S/N > 10) biotin on-column, respectively. The LC/ELSD method exhibits good linearity from 155 ng to 9900 ng biotin on-column with a method LOD and LOQ of 155 ng (S/N > 3) and 310 ng (S/N > 10) biotin on-column, respectively. Method performance data indicates that the LC/MS method is analytically superior to the LC/ELSD method; however, either method in combination with SRM 3280 should provide quality assurance, accuracy, and traceability for biotin levels in multivitamin/multielement dietary supplements.     

Determination of aflatoxins in high-pigment content samples by matrix solid-phase dispersion and high-performance liquid chromatography

A fast, efficient, and cost-effective method was developed for the analysis of aflatoxins in farm commodities with high-pigment content, such as chili powder, green bean, and black sesame. The proposed method involved matrix solid-phase dispersion (MSPD) and high-performance liquid chromatography (HPLC)-fluorescence detection (FLD) with postcolumn electrochemical derivatization in a Kobra cell. The MSPD procedure combined the extraction with neutral alumina and pigment cleanup with graphitic carbon black (GCB) in a single step. The recoveries of aflatoxins ranged from 88% to 95% with the relative standard deviations (RSD) less than 6% (n = 6). The limits of detection (LODs) were 0.25 ng/g aflatoxin B1, G1, and 0.10 ng/g aflatoxin B2, G2, respectively. The analytical results obtained by MSPD were compared to those of the immunoaffinity column (IAC) cleanup method. No significant differences were found between the two methods by t-test at the 95% confidence level.     

磷脂酶D催化转碱基中磷脂的分析

报道了一种采用梯度洗脱系统和蒸发光散射检测器,通过HPLC/ELSD同时分析测定磷脂酰甘油（PG）、磷脂酰丝氨酸（PS）、磷脂酰胆碱（PC）和磷脂酸（PA）的方法。该方法稳定可靠,PG、PS、PC、PA全部达到基线分离,可用于PG、PS、PC、PA的同时测定。     

An evaluation of methods for measurement of pesticides in sorption experiments

Abstract

The concentration of four pesticides (2,4‐D, atrazine, phorate, and terbufos) in soil solution during sorption experiments was measured using UV spectrophotometry, Gas Liquid Chromatography (GLC), High Performance Liquid Chromatography (HPLC), and radiotracer technique. The presence of water soluble organic matter in soil solution interfered with the measurement of pesticide using the UV spectrophotometry. The use of GLC, HPLC, and radiotracer technique involving ¹⁴C gave a good estimate of the concentration of pesticide in soil solution. The pesticide remaining in soil can be quantitatively analyzed by extracting with a scintillation solution containing an organic solvent such as toluene or dioxane. Among the various centrifuge tubes glass tubes with Teflon caps sorbed negligible amount of pesticides and these tubes can be used for the sorption measurements.     

Comparison of various extraction methods for policosanol from rice bran wax and establishment of chromatographic fingerprint of policosanol

A capillary gas chromatographic (GC) method has been developed for the separation and determination of policosanol components extracted from rice bran wax. A Varian CP-sil 8 CB column was employed, and an oven temperature was programmed. Gas chromatography-mass spectrometry (GC-MS) was used to identify the composition of policosanol. Quantitative analysis was carried out by means of hydrogen flame ionization detector (FID) with dinonyl phthalate (DNP) as internal standard. The results indicated that the extract obtained by dry saponification has the highest contents of octacosanol and triacontanol among extracts by all used extraction methods including dry saponification, saponification in alcohol, saponification in water (neutralized and non-neutralized), and transesterification. Meanwhile, the GC-MS fingerprint of policosanol extracted by dry saponification has been established. Euclidean distance similarity calculation showed remarkable consistency of compositions and contents among 12 batches of policosanol from a rice bran wax variety. This protocol provided a rapid and feasible method for quality control of policosanol products.     

Fate of Chlorinated Benzenes in Laboratory Peat and Pozzolana Filters

The removal of chlorinated benzenes (CBs) from the compartments and from polluted industrial sites is of great public interest for the decontamination of polluted water and for the protection of the environment. Biological degradation could be considered as a feasible process to eliminate these compounds from the environment as soil or groundwater. A research program in progress since the year 2007 was initiated to investigate the capacity of eco-remediation of CB-contaminated groundwater using a pilot-scale subsurface flow constructed wetland. In order to assess the removal efficiency of these compounds and to evaluate the biological activities, column experiments were performed. The fate of three CBs was investigated by feeding spiked tap water through laboratory columns filled with two different solid-state materials: peat and pozzolana. In order to stimulate biological activity, organic matter coming from aged vertical flow constructed wetland was added to the media. Concentrations of CBs in water effluent and in air and biological activities were monitored during 4 months. At the end of the experimental period, CB concentrations in the depth of columns were determined and a mass balance was calculated for the CBs. Removal efficiencies of the laboratory columns were >98% in the peat columns and situated around 87% to 95% in the pozzolana columns, indicating the suitability of the experimental systems for the removal of CBs. Higher effluent CB concentrations from the pozzolana columns were detected. Concentration of CBs in ambient air indicates that volatilization was low. ATP monitoring, reduction of tetrazolium violet, and exopolysaccharide determination indicated considerable biological activity with variations according to column depth and carrier material.     

Capillary gas chromatographic analysis of amino acids by enantiomer labeling

The optical isomers of amino acids can be easily separated by gas chromatography using capillary columns coated with the chiral polysiloxane peptide, Chirasil-Val. Quantitative trace amino acid analysis in complex mixtures such as biological fluids, sea water, or protein hydrolysates can be achieved by enantiomer labeling: The D-amino acid enantiomers, which do not occur naturally, are added to the sample prior to analysis as internal standards. Because the D-enantiomers show the same physical and chemical properties as the natural L-enantiomers, they are ideal standard references. In routine analysis, the derivatization is achieved with a new automated derivatization robot. The D-standard serves as overall internal standard for the whole analytical procedure from sample enrichment to derivatization, chromatography, and response of the detector.     

The effect of temperature‐induced soil water repellency on transient capillary pressure–water content relations during capillary rise

Long‐term capillary rise experiments (0 to about 89 000 hour) were performed at 19°C on homogenized and heat‐treated podsolic forest top‐ and subsoil samples. These were packed into columns, the bases of which were then partially immersed, at constant depth, in water reservoirs to simulate a constant water table. Selected columns were equipped with tensiometer and TDR probes. Other columns were removed at prescribed times and divided into 2‐cm horizontal segments whose volumetric water contents were determined. The degree of saturation was then estimated by comparison with the capillary rise in duplicate arrangements of samples immersed in ethanol. It was found that the heat treatments conferred increased water repellency (WR) on the soil, which increased with temperature (significantly so at greater than 60°C). This had a profound effect on the capillary rise characteristics and development of water content in the soil behind the wetting front, indicating an effective, albeit slow, reduction in effective WR. This has implications for hydraulic modelling of soils with significant WR and demonstrates that sub‐surface WR exerts a significant influence on capillary rise from a water table and suggests that commonly used indicators of surface WR using droplet tests may not be useful for such modelling purposes.