[Detection of Residual Solvents in Commercial Supplements Using Headspace (HS)-GC-MS].

In order to understand the actual state of residual solvents contained in commercial supplements, we performed a simultaneous analysis of residual solvents by headspace (HS)-GC-MS with reference to the Japanese Pharmacopoeia's "Residual Solvents", for 29 products selected from among commercial supplements (e.g., revitalizers, weight loss pills) that are deeply colored or contain coating agents and extract powder. As a result, benzene (class 1) was detected in eight black-colored supplements, and hexane (class 2B) was also detected in one of those products. On the other hand, methanol (class 2A) was detected in four products containing coating agents and extract powders, such as citrus peel extract. None of these residual solvents exceeded the concentration limits set by the Japanese Pharmacopoeia. Benzene was detected at 1.7 µg/g, which was near the concentration limit, in some products. As raw materials used for the manufacture of the black-colored supplements from which benzene was detected commonly included activated carbon, we analyzed the residual solvents contained in activated carbon commercially available for use as food additive and in food production and medicine. As a result, benzene was detected at high concentrations in activated carbon made from hemp (approximately 29 µg/g) and bamboo (approximately 140 µg/g).

Headspace GC/MS Analysis of Residual Solvents in Dietary Supplements, Cosmetics, and Household Products Using Ethyl Lactate as a Dissolution Medium.

BACKGROUND: The static headspace technique is one of the most popular techniques for residual solvent analysis and dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) are widely use as the dissolution media. OBJECTIVE: This study aims to establish ethyl lactate (EL), a solvent with low toxicity and less environmental impact, as an alternative dissolution medium to DMSO and DMF for the static headspace analysis of toxic residual solvents in food, cosmetics, and similar complex organic matrices. METHODS: Samples (a sample of dietary supplement and two samples each of cosmetics and household products) spiked with benzene, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethene, and 1,1,1-trichloroethane were dissolved in EL, DMSO, and DMF. Static headspace GC/MS and the standard addition method were used to detect and quantify the residual solvents. RESULTS: The dissolution and dispersion of these samples, especially the ones which were water-insoluble, were better than those in DMSO and DMF. The recoveries, except that of benzene in an aerosol spray, in EL ranged from 77 to 110%. The relative SDs in EL ranged from 2.5 to 11% and were better or equivalent to those in DMSO and DMF. CONCLUSIONS: EL was suitable as the dissolution medium for such samples, which may contain large amounts of organic solvents or various ingredients, in static headspace GC/MS analysis of residual solvents.

Mass Spectrometric Analysis of Synthetic Organic Pigments.

Though synthetic organic colorants are used in various applications nowadays, there is the concern that impurities by-produced during the manufacturing and degradation products in some of these colorants are persistent organic pollutants and carcinogens. Thus, it is important to identify the synthetic organic colorants in various products, such as commercial paints, ink, cosmetics, food, textile, and plastics. Dyes, which are soluble in water and other solvents, could be analyzed by chromatographic methods. In contrast, it is difficult to analyze synthetic organic pigments by these methods because of their insolubility. This review is an overview of mass spectrometric analysis of synthetic organic pigments by various ionization methods. We highlight a recent study of textile samples by atmospheric pressure solid analysis probe MS. Furthermore, the mass spectral features of synthetic organic pigments and their separation from other components such as paint media and plasticizers are discussed.

Analysis of Primary Aromatic Amines Derived from Azo Colorants in Textile Products and Determination of Their Source Colorant.

Twenty-four primary aromatic amines (PAAs) derived from azo colorants, which are controlled by the Act on Control of Household Products Containing Harmful Substances by the Japan Ministry of Health, Labour and Welfare, aniline and 1,4-phenylendiamine were analyzed in 86 samples of 40 textile products by GC-MS. Even though these PAAs detected in the samples did not exceed the regulation value (30 µg/g), 14 kinds of PAAs were detected that exceeded the limit of quantification. 4,4'-Methylenedianiline, in amounts that exceeded the limit of quantification, was detected in 20 textile samples containing synthesis fiber (16 samples made from polyurethane, two samples made from polyester, and two samples made from acryl); however, it was not detected in natural fiber textile samples. Of these samples, 4,4'-methylenedianiline was detected in 16 out of 19 samples (84%) made from polyurethane fiber. This suggests that 4,4'-methylenedianiline is formed from polyurethane. The origin of 3,3'-dichlorobenzidine was investigated in three samples releasing more than 3 µg/g (3.9-15 µg/g) of 3,3'-dichlorobenzidine using atmospheric pressure solids analysis probe-mass spectrometry and Pigment Orange 13 was identified as the orange colorant in the textile printing parts. This result suggests that 3,3'-dichlorobenzidine detected in these three samples was generated by the reduction of Pigment Orange 13.

Identification of indicator components for the discrimination of Cassia plants in health teas and development of analytical method for the components.

Components that could be used as indicators for the discrimination of senna (Cassia angustifolia) from other cassia plants contained in health teas were identified, and an analytical method for the components was developed. Our results revealed two components in senna that were not found in other Cassia spp. widely used in health teas, such as C. alata, C. corymbosa, C. obtusifolia, and C. occidentalis. Structural elucidation of the two components showed that they were isorhamnetin-3-O-gentiobioside and tinnevellin glucoside. We analyzed commercial health teas using the HPLC method developed in this study. The two indicator components were detected at 366 nm using an RP C18 column and gradient elution with a mixture of water and acetonitrile (with formic acid), as the mobile phase. Our analytical method by HPLC enabled the differentiation of senna from other Cassia plants present in health teas in which sennosides A and B were detected. Moreover, this method allowed us to predict the parts of senna in health teas from the amounts of isorhamnetin-3-O-gentiobioside and tinnevellin glucoside contained in the teas.

[Study on processed senna found in health teas].

Sennoside A and B were detected in 21 commercial health tea products surveyed in 2000-2007, but there were 8 products in which the leaves could not be identified as senna because the leaves had become discolored. The results of assay of sennoside levels and TLC chromatograms suggested that processed senna had been used in these products. Next, with reference to tea and health tea manufacturing methods, pharmaceutical senna was roasted or wet-processed experimentally. The results indicated that the discolored leaves contained in commercial health tea were most likely derived from senna leaves. Moreover, sennosides in medicinal doses were detected in some processed senna samples, and were determined to have a cathartic action in mice. Based on morphological confirmation and the results of component analysis, including sennoside, the discolored leaves found in commercial health teas were therefore determined to be senna leaves. There may be possible health risks, including diarrhea.

Development of a headspace GC/MS analysis for carbonyl compounds (aldehydes and ketones) in household products after derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine.

Carbonyl compounds (aldehydes and ketones) are suspected to be among the chemical compounds responsible for Sick Building Syndrome and Multiple Chemical Sensitivities. A headspace gas chromatography/mass spectrometry (GC/MS) analysis for these compounds was developed using derivatization of the compounds into volatile derivatives with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). For GC/MS detection, two ionization modes including electron impact ionization (EI) and negative chemical ionization (NCI) were compared. The NCI mode seemed to be better because of its higher selectivity and sensitivity. This headspace GC/MS (NCI mode) was employed as analysis for aldehydes and ketones in materials (fiber products, adhesives, and printed materials). Formaldehyde was detected in the range of N.D. (not detected) to 39 microg/g; acetaldehyde, N.D. to 4.1 microg/g; propionaldehyde, N.D. to 1.0 microg/g; n-butyraldehyde, N.D. to 0.10 microg/g; and acetone, N.D. to 3.1 microg/g in the samples analyzed.