Determination of coumarin in fragrance products by capillary gas chromatography with electron capture detection.

A gas chromatographic (GC) method is described for the determination of coumarin in fragrance products. Coumarin was tentatively identified by retention time and confirmed by GC/mass spectrometry. The amount of coumarin was determined by external standard. The method was validated by conducting recovery studies from fortified fragrance products at several concentrations. Recoveries of coumarin ranged from 99 to 110%, with a relative standard deviation of 3.24. The method was used to survey a variety of fragrance products purchased in the metropolitan Washington, DC area, for coumarin. Seventy one percent of the products were found to contain coumarin at concentrations ranging from 0.002 to 0.61%.

Determination of musk ambrette, musk xylol, and musk ketone in fragrance products by capillary gas chromatography with electron capture detection.

A gas chromatographic method using a capillary column with electron capture detection was developed for the simultaneous determination of 3 nitromusk fragrance ingredients: musk ambrette (MA), musk xylol (MX), and musk ketone (MK), in fragrance products. The accuracy of the method was determined by recovery of each nitromusk from fortified fragrance products at 3 different concentrations. Recoveries ranged from 95.0 to 105.9% for MA, 88.4 to 102.5% for MX, and 93.7 to 103.7% for MK. The method was used to survey 30 fragrance products purchased in the Washington, DC, area for each of the nitromusks. MA was not found in any of the products. MX was found in 9 products at levels ranging from 0.001 to 0.22%; MK was found in 8 products at levels ranging from 0.023 to 0.45%. The presence of MX and MK was confirmed by gas chromatography/mass spectrometry in many of the fragrance products.

Determination of musk ambrette in fragrance products by capillary gas chromatography with electron capture detection: interlaboratory study.

A gas chromatographic method that uses an internal standard additions techniques is described for the determination of musck ambrette (MA) in fragrance products. A solution containing the product and a known amount of an internal standard, musk tibetene (MT), is injected directly into a gas chromatograph equipped with an electron capture detector. The chromatographic separation of the components on a wide-bore fused silica capillary column is recorded and a response constant is calculated from MA and MT peak heights. A similar response constant is also calculated for a standard solution containing known concentrations of MA and MT. The MA content of the fragrance product is then calculated. Average recoveries of MA from fragrance products ranged from 97.6 to 102.3%. The method was also evaluated collaboratively by 6 laboratories. In this study, the reproducibility relative standard deviation for MA in 6 fragrance test samples ranged from 2.78 to 22.87%.

Liquid chromatographic-fluorometric determination of cinnamyl alcohol in perfumes, colognes, and toilet waters.

A liquid chromatographic (LC) method is described for the determination of cinnamyl alcohol (3-phenyl-2-propen-1-ol) in fragrance compositions. The fragrance product is partially cleaned up by diluting the fragrance with a 95% ethanol-water mixture and passing it through a short column containing RP-8 packing. An aliquot of the effluent is then analyzed by LC using an RP-18 column interfaced to a spectrophotofluorometer equipped with double monochromators. The fluorescence emission intensity of the eluted cinnamyl alcohol is measured and compared with that of a standard to calculate the amount of cinnamyl alcohol present. Recoveries from fragrance products fortified with cinnamyl alcohol at levels ranging from 0.0020 to 0.060 mg/mL ranged from 85 to 105% with a mean of 94%. The lowest level of determination was 0.0005 mg/mL.

Liquid chromatographic separation and fluorometric determination of cis- and trans-isoeugenol in perfumes, colognes, and toilet waters.

A liquid chromatographic (LC)-fluorometric method is described for the determination of cis- and trans-isoeugenol (2-methoxy-4-propenylphenol) in perfumes, colognes, and toilet waters. A test portion of the product is added to diethyl ether, and the isoeugenol isomers are extracted with sodium hydroxide solution. The basic extract is then acidified, and the isoeugenol isomers are extracted with isooctane. Aliquots of the isooctane extract are analyzed by using a silver ion cation exchange LC column interfaced to a spectrophotofluorometer. Each isomer in the product is determined by comparing its fluorescence emission intensity with that of an external standard consisting of a mixture of both isomers in which the relative concentration of each has been determined. Average recoveries from various commercial fragrances fortified with a mixture of cis- and trans-isoeugenol with total isoeugenol content of 0.1, 0.5, and 4.0 mg/mL ranged from 87 to 105% for the trans-isomer (SD = 4.6%) and from 83 to 113% for the cis-isomer (SD = 6.7%). The limit of determination is approximately 0.002 mg/mL.

High-performance liquid chromatographic-fluorometric determination of cinnamaldehyde in perfume, cologne and toilet water.

A high-performance liquid chromatographic (HPLC)-fluorometric method is described for the determination of trans-cinnamaldehyde in fragrances. The fragrance is added to isooctane and extracted with an aqueous solution of the sodium salt of 6-aminocaproic acid to isolate the aldehyde fraction. After dilution with water, an aliquot of the extract is added to a solution of 1,2-diaminonaphthalene monosulfate in dilute formic acid. The fluorescent derivative of cinnamaldehyde, 2-styrylnaphth[1,2-d]imidazole, is prepared by incubating and then cooling the solution and adding pyridine. Aliquots of the fluorophore solution are analyzed on a reversed-phase C18 HPLC column by using a buffered tetrahydrofuran-water eluent. Cinnamaldehyde is quantitated by comparing fluorescence emission intensity with that of a standard. Recoveries from samples of various commercial fragrances, spiked with cinnamaldehyde at the 0.01, 0.05 and 0.1% levels, ranged from 94 to 112% with a mean of 103% and a standard deviation of 5.3. The limit of detection is approximately 1 ng.

High pressure liquid chromatographic-thermal energy determination of N-nitrosodiethanolamine in cosmetics.

Methods for the determination and confirmation of N-nitrosodiethanolamine (NDELA) in cosmetic products were developed. The NDELA fraction was isolated from a cosmetic product by a series of solvent extractions which were designed to concentrate the NDELA and remove ingredients deleterious to the analytical system. The isolated fraction was then analyzed for NDELA using a high pressure liquid chromatograph (HPLC) interfaced with a thermal energy analyzer (TEA). The compound was measured by comparison of detector response with those of known standards. NDELA was verified by gas chromatography-mass spectrometry of the silyl derivative after preliminary cleanup of the sample by gradient elution HPLC on a Partisil 10 PAC column. The limit of detection of NDELA by TEA is 2-3 ng, which corresponds to 20-30 ppb in the cosmetic product. Analysis of an emulsion cream and a hair grooming gel spiked at 3 and 4 ng concentration levels, respectively, yielded recoveries ranging from 71 to 103% (average 88%).

Determination of bergapten in fragrance preparations by thin layer chromatography and spectrophotofluorometry.

A method has been developed for the determination of bergapten (5-methoxypsoralen), a known phototoxin, in perfumes,colognes, and toilet waters. The bergapten and other lactonic compounds were first isolated from the sample by a series of extractions. The extract containing the bergapten was diluted to a known volume and a aliquot was spotted on a thin layer chromatographic (TLC) plate coated with silica gel G. After 2-dimensional development with hexane - carbon tetrachloride - tert - butylamine (180+12+9) and hexane-toluene-ethyl acetate-acetic acid (100+10+15+0.5), the TLC plate was dried and the emitted fluorescence of bergapten was measured, using a spectrophotofluorometer equipped with a TLC accessory and coupled to an automatic digital integrator. The amount of bergapten was determined by comparing its peak area to those of bergapten standards. The average recovery for levels of 0.001, 0.005, and 0.01% bergapten was 88%.