Collaborative study of the determination of boric acid in caviar by emission spectroscopy.

Caviar samples were spiked at the 0.1 and 0.2% levels and digested with nitric acid in a closed Teflon-lined digestion vessel to prevent volatility losses. The boron was complexed with 2-ethyl-1,3-hexanediol and extracted into methylisobulty ketone. The emission of the boron oxide band was measured in a nitrous oxidehydrogen flame. The mean recoveries at the 0.1 and 0.2% levels for 6 collaborators were 95.7 and 97.1%, respectively.     

Colorimetric determination of mestranol in combination with ethynodiol diacetate.

Mestranol in combination with ethynodiol diacetate, an oral contraceptive formulation, is isolated from the sample on a partition chromatographic column prior to colorimetric determination. The color reaction which is specific for estrogens is formed by shaking an aliquot of the heptane eluate of mestranol with a 30% methanol-sulfuric acid solution. A collaborative study of the method gave results of 99.8% of added mestranol for the simulated mix and 100.7% of labelled mestranol for the commercial tablet. The method has been adopted as official first aciton.     

Colorimetric determination of poly(N-vinyl-2-pyrrolidone) in contact lens solutions.

A rapid colorimetric method is presented for the quantitative determination of poly(N-vinyl-2-pyrrolidone) in contact lens solutions. The method is simple, requires no sample pretreatment, and uses only a small volume of sample. The procedure is based on the measurement of the net absorbance of a poly(N-vinyl-2-pyrrolidone)- Congo red complex at 545 nm. An accuracy of greater than +/- 4% was obtained for the concetnration ranges usually found in contact lens solutions with a minimum detection level of 10 ppm. The method is useful as a screening procedure for solutions of unknown composition and as a quality assurance procedure for routine determinations.     

Distribution of bromophenols in species of marine polychaetes and bryozoans from eastern Australia and the role of such animals in the flavor of edible ocean fish and prawns (shrimp).

Sixteen species (44 samples) of marine polychaetes and 10 species (14 samples) of bryozoans from eastern Australia were analyzed by GC/MS for the key seafood flavor components 2- and 4-bromophenol, 2, 4- and 2,6-dibromophenol, and 2,4,6-tribromophenol. All five bromophenols were found in 91% of polychaetes and 64% of bryozoans. The remaining samples all contained at least three bromophenols. 2,4, 6-Tribromophenol was found in all polychaetes and bryozoans and, with few exceptions, was present in the highest concentrations. The total bromophenol content determined on a wet-weight basis varied widely between species: for polychaetes, from 58 ng/g for Australonuphis teres to 8.3 million ng/g for Barantolla lepte, and for bryozoans, from 36 ng/g for Cladostephus spongiosus to 1668 ng/g for Amathia wilsoni. Species of polychaetes with the highest concentrations of bromophenols were all collected from muddy environments. The possible effects that dietary polychaetes and bryozoans have on the ocean-, brine-, or iodine-like flavors of certain seafoods are discussed.     

Determination of total N-nitroso compounds and their precursors in frankfurters, fresh meat, dried salted fish, sauces, tobacco, and tobacco smoke particulates.

Total N-nitroso compounds (NOC) and NOC precursors (NOCP) were determined in extracts of food and tobacco products. Following Walters' method, NOC were decomposed to NO with refluxing HBr/HCl/HOAc/EtOAc and NO was measured by chemiluminescence. NOC were determined after sulfamic acid treatment to destroy nitrite, and NOCP were determined after treatment with 110 mM nitrite and then sulfamic acid. Analysis without HBr gave results < or =20% of those with HBr. This NOC method was efficient for nitrosamines but not nitrosoureas. The standard nitrosation for determining NOCP gave high yields for readily nitrosated amines, including 1-deoxy-1-fructosylvaline, but not for simple amines, dipeptides, and alkylureas. Mean NOC and NOCP results were (respectively, in micromol/kg of product) 5.5 and 2700 for frankfurters, 0.5 and 660 for fresh meat, 5.8 and 5800 for salted, dried fish, and 660 and 2900 for chewing tobacco (all for aqueous extracts) and 220 and 20000 nmol/cigarette for MeCN extracts of cigarette smoke filter pads.     

Analysis of 2-alkylcyclobutanones with accelerated solvent extraction to detect irradiated meat and fish

A new analytical procedure has been developed to analyze 2-alkylcyclobutanones to detect gamma-ray-irradiated fat-containing foodstuffs. Samples were extracted with an accelerated solvent extraction system via hot and pressurized ethyl acetate in cells. A large amount of fat in the extract was precipitated and removed with filtration by standing at -20 degrees C after the addition of acetonitrile. The extract was further cleaned with a 1 g silica gel mini column, and the radiolytic compounds of 2-docecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were determined with gas chromatography with mass spectrometry (GC/MS). Sample preparation time before GC/MS was 7-8 h. At first, the procedure was evaluated with a recovery test in eight samples spiked with 2-DCB and 2-TCB at 20 ng/g, resulting in 70-105% recoveries with mostly less than 10% relative standard deviations. The procedure was further evaluated with beef, pork, chicken, and salmon samples irradiated with gamma-rays from 0.7 to 7.0 kGy at -19 degrees C. Both 2-DCB and 2-TCB in most samples were detected with good dose-response relations at all doses, while salmon was detected more than 2 kGy irradiation. The amounts of 2-alkylcyclobutanones produced reflected precursor fatty acids levels in samples, especially for the combination of 2-TCB and stearic acid. The results indicated that the production rate of 2-TCB to stearic acid was more obvious than that of 2-DCB to palmitic acid in frozen samples with gamma-ray irradiation.     

Colorimetric and spectrophotometric determination of total and non-phenolic alkaloids in ipeca and its formulations.

A simple method, requiring no chromatographic separation, is presented for the determination of the total and non-phenolic alkaloids in ipeca and its preparations. The complex formed between the alkaloid and methyl orange at pH 5.0 is extracted with chloroform and treated with 0.1N NaOH. The liberated dye, determined at 460 nm, is a measure of the total alkaloids. The chloroform phase remaining is treated with 0.1N H2SO4, and the acid extract is measured at 283 nm for the non-phenolic alkaloids, calculated as emetine. The proposed method was successfully applied to samples of ipeca powder, ipeca tincture, and 3 British Pharmaceutical Codex mixtures containing ipeca tincture, namely, ipecacuanha mixture, pediatric; ipecacuanha and ammonia mixture, pediatric; and belladonna and ipecacuanha mixture, pediatric. The proposed method compares favorably with the Egyptian Pharmacopoeia, British Pharmacopoeia, and USP methods and has a relative standard deviation of 1.54%. The present procedure is less time-consuming and requires about 45 and 90 min for the assay of ipeca tincture and powder, respectively. Only a small sample (0.2 mL tincture of 1.0 g powder) is required.     

Liquid chromatographic determination of L-ascorbate 2-polyphosphate in fish feeds by enzymatic release of L-ascorbate

An accurate method was devised to assay L-ascorbic 2-polyphosphate esters (AsPP) in fish feed by phosphatase digestion followed by determination of the released L-ascorbic acid (AsA). Compressed yeast and dithiothreitol are added to the phosphatase reaction mixture to give 95-100% recovery of AsA, which is quantitated by reverse-phase liquid chromatography (LC) with electrochemical detection. Chromatograms of all feed digests showed baseline resolution of AsA. In 3 feeds, to which 75-125 ppm AsA equivalents in the form of AsPP were added, the assay procedure gave 98-100% recovery of AsA.     

Analysis of patulin in apple juice by diphasic dialysis extraction with in situ acylation and mass spectrometric determination.

A procedure combining diphasic dialysis extraction with in situ acylation and gas chromatography/mass spectrometry (GC/MS) determination was developed for detection and quantification of the mycotoxin patulin in apple juice. Apple juice samples spiked with 4-N,N-dimethylaminopyridine were dialyzed using methane chloride and acetic anhydride inside dialysis tubing. Patulin was derivatized into its acetate and collected in the tubing after diphasic dialysis and was directly determined using GC/MS with the selective ion monitoring mode without further concentration and cleanup steps. Quantification was carried out by a calibration curve with an internal standard of correlation. The appropriate parameters of both dialysis and derivatization were examined. The linear range of the calibration curve was found to be 10-250 microg/L for patulin, and the limit of quantification was 10 microg/L. Levels of patulin ranging from 0 to 107.2 microg/L with 77-109% recovery were found in 10 apple samples. The technique combining diphasic dialysis extraction and acylation was demonstrated and showed potential for other applications.     

Separation and determination of diesel contaminants in various fish products by capillary gas chromatography.

A semiquantitative capillary column gas chromatographic method is described for the determination of diesel fuel contamination in various canned seafood products. The diesel contaminants are separated from the fish sample by steam distillation, with little carry-over of interfering intrinsic materials such as fish oils. The diesel fuel is extracted from the condensate with n-hexane, and the extract is analyzed on an SPB-1 fused silica capillary column. The efficiency of recovery of diesel fuel added to canned seafood at levels of 40-400 ppt ranged from 72 to 102%. With the additional step of concentrating the hexane extract, the sensitivity of this procedure may be increased at least 10-fold. This procedure can detect the differences among diesel fuel grades No. 1, 2, and 5, and variations within diesel grade No. 2, and thus may be useful in determining the type of petroleum contaminants present in various canned fish products.     

Colorimetric and gas-liquid chromatographic determination of atropine-hyoscyamine and hyoscine (scopolamine) in solanaceous plants.

Two colorimetric micromethods are described for the determination of atropine-hyoscyamine and hyoscine (scopolamine), using p-dimethylaminobenzaldehyde and citric acid-acetic anhydride as the color reagents. These methods are sensitive to 60-1200 and 10-360 mug alkaloid/10 ml. The colorimetric methods were also successfully applied after a preliminary thin layer chromatographic separation of the alkaloids. A gas-liquid chromatographic procedure was also developed, which yielded comparable results with the colorimetric methods.     

Simplified fat extraction with sulfuric acid as cleanup procedure for residue determination of chlorinated hydrocarbons in butter

A new cleanup procedure is described for chlorinated hydrocarbon residues in butterfat. The method is based on the dropwise addition of H2SO4 to a fat solution column and continuous removal of the lipids and the acid. The cleanup of 0.25-2.0 g fat requires only 10-40 ml sulfuric acid and 12-17 ml petroleum ether. There is no need for any further cleanup step, solvent evaporation, or centrifugation. The method is easy to standardize and is suitable for automation. At least 30 fat samples can be cleaned up manually by one analyst in one day. Recoveries were complete (greater than 90%) for polychlorinated biphenyl compounds and for 13 chlorinated pesticides of 16 examined. The method was tested on chlorinated hydrocarbon residues in commercial butter and the results were compared with those obtained with the acetonitrile method. The versatility and limitations of the method were investigated by varying the sulfuric acid strength, initial fat solution concentration, and column dimensions.     

The determination of cadmium in soils,plants and fertilizers by dithizone extraction and atomic absorption spectroscopy

Abstract

Methods are proposed for the determination of cadmium in soils, plants and fertilizers.

Soil is first dissolved by treatment with hydrofluoric and hydrochloric acids and plant material is digested with nitric‐perchloric‐sulphuric acids. The cadmium is then extracted from the resulting solutions as the dithizone complex. After destruction of the dithizone the cadmium is dissolved in dilute hydrochloric acid and determined by atomic absorption spectroscopy. Cadmium in phosphatic fertilizers is determined directly by atomic absorption measurement on hydrochloric acid digests of the fertilizer.

The proposed methods have precision adequate for the study of cadmium in soil‐plant systems, the limits of detection being: plant material, 0.004 ppm Cd; soils, 0.02 ppm; and phosphatic fertilizers, 1 ppm.     

Assay of calcium borogluconate veterinary medicines for calcium gluconate, boric acid, phosphorus, and magnesium by using inductively coupled plasma emission spectrometry

An inductively coupled plasma spectrometric method is described for the determination of 4 elements (Ca, B, P, and Mg) in calcium borogluconate veterinary medicines. Samples are diluted, acidified, and sprayed directly into the plasma. Reproducibility relative confidence intervals for a single sample assay are +/- 1.4% (calcium), +/- 1.8% (boron), +/- 2.6% (phosphorus), and +/- 1.4% (magnesium). The total element concentrations for each of 4 elements compared favorably with concentrations determined by alternative methods. Formulation estimates of levels of calcium gluconate, boric acid, phosphorus, and magnesium salts can be made from the analytical data.     

Extraction and determination by gas chromatography of S,S,S-tri-n-butyl phosphorotrithioate (DEF) in fish and water

A simple, low-cost, fast method for the extraction and cleanup of DEF (S,S,S-tri-n-butyl phosphorotrithioate) from fish tissues and water samples was developed. The method combines extraction and cleanup in one step. The basis of the method is passing water samples or aqueous tissue homogenates containing DEF through a C-18 disposable cartridge. DEF is eluted from the cartridge by acetone or ethyl acetate. The eluates are analyzed by gas chromatography using a thermionic-specific detector. The method detects levels as low as 100 parts per trillion (ppt) in water samples; recovery efficiency from spiked fish tissues was greater than 95%. In addition, detectable levels of DEF were recovered from liver, brain, and muscle tissue of fish exposed to this compound. The method has a potential for use with other pesticides.     

Simultaneous determination of trace levels of 10 quinolones in swine, chicken, and shrimp muscle tissues using HPLC with programmable fluorescence detection

A HPLC method using a modified sample preparation procedure was optimized and validated for the quantification of 10 quinolones (QNs), including marbofloxacin, ciprofloxacin, norfloxacin, lomefloxacin, danofloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid, and flumequine, in swine, chicken, and shrimp tissues. In this method, only a small mass (相似文献   

Gas-liquid chromatographics determination of Bayer 73 in fish, aquatic invertebrates, mud, and water

A gas-liquid chromatographic (GLC) method is described for determining residues of Bayer 73 (2-aminoethanol salt of 2',5-dichloro-4'-nitrosalicylanilide) in fish muscle, aquatic invertebrates, mud, and water by analyzing for 2-chloro-4-nitroaniline (CNA), a hydrolysis product of Bayer 73. Bayer 73 residues are extracted from fish muscle tissue, invertebrates, and mud with acetone-formic acid (98+2), and partitioned from water samples with chloroform. After sample cleanup by solvent and acid-base partitioning, the concentrated extract is hydrolyzed with 2N NaOH and H2O2 for 10 min at 95 degrees C. The CNA is then partitioned into hexane-ethyl ether (7+3) and determined by electron capture GLC. Average recoveries were 88% for fish, 82% for invertebrates, 82% for mud, and 98% for water at 3 or more fortification levels.     

Structural determination and odor characterization of N-(2-mercaptoethyl)-1,3-thiazolidine,a new intense popcorn-like-smelling odorant

The chemical structure of a novel, roasty, popcorn-like-smelling aroma compound formed from the reaction of fructose with cysteamine was studied by high-resolution mass spectrometry and nuclear magnetic resonance experiments. The structure of N-(2-mercaptoethyl)-1,3-thiazolidine exhibiting the extremely low odor threshold of 0.005 ng/L in air was finally confirmed by synthesis.     

Solid-phase extraction followed by liquid chromatography-mass spectrometry for trace determination of beta-lactam antibiotics in bovine milk.

A confirmatory assay able to unambiguously identify and quantify 10 approved-for-use beta-lactam antibiotics in milk below stipulated U.S. and EU tolerance levels is presented. beta-Lactams are extracted from 10 mL of intact milk by a Carbograph 4 cartridge. After solvent removal, residue reconstitution, and filtration, a completely transparent and uncolored extract is injected into a liquid chromatography -mass spectrometry (LC-MS) instrument equipped with an electrospray (ES) ion source and a single quadrupole. During the chromatographic run, the ES/MS system is operated first in the positive-ion mode (PI) and then in the negative-ion (NI) mode. This is done to circumvent matrix interferences resulting in remarkable signal weakening of the last-eluted analytes, when detecting them as [M+H]+ adduct ions. MS data acquisition is performed by a time-scheduled three-ion selected ion monitoring program. At the 5 ng/mL level, recoveries of the beta-lactams are between 70 (nafcillin) and 108% (cephalin), with relative standard deviations ranging between 5 (oxacillin) and 11% (amoxicillin and ceftiofur). The response of the ES/MS detector is linearly related to injected amounts up to 500 ng, irrespective of the chemical characteristics of the beta-lactams and the acquisition mode selected (PI or NI modes). Limits of quantification, based on a minimal value of the signal-to-noise ratio of 10, were estimated to be within 0.4 (cephalin) and 3 ng/mL (dicloxacillin). Analyses of milk samples taken after intramammary application of amoxicillin showed that 1.2 ng/mL of this penicillin was still present 6 days after treatment. At this concentration level, the identification power of the method is not weakened, as signals of the three product ions of amoxicillin are still well distinguishable from the background noise.