Development and validation of multiresidue method for organophosphorus pesticides in lanolin using gas chromatography-tandem mass spectrometry.

Lanolin, also known as wool wax, is derived from sheep and has diverse applications in food, cosmetic, textile and lubricant industries. Owing to its direct contact with human, there is a need of studying pesticide residues as contaminants in lanolin. The present study describes a single novel hyphenated gas chromatography-tandem mass spectrometry (GC-MS/MS) technique for the quantification of 14 organophosphorus (OP) pesticides (tecnazene, propetamphos, diazinon, dichlofenthion, chlorpyrifos methyl, fenchlorphos, malathion, chlorpyrifos, pirimiphos ethyl, bromophos ethyl, tetrachlorvinphos, ethion, phosalone, and coumaphos) in lanolin using electrospray ionization (EI) with multiple reaction monitoring (MRM) acquisition mode. The method is simple in terms of sample preparation steps based on matrix solid-phase dispersion (MSPD). The method was found to be linear over the analytical range of 0.05-2.0 µg/g, with acceptable coefficient of determination (r2  ≥ 0.99) for all the 14 pesticides. The limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be less than 0.05 and 0.1 µg/g, respectively, for all the 14 OP pesticide residues. The precision and accuracy of the method were found to be within the acceptable limits, that is, recoveries in the range of 83.5%-104.1% with less than 12.5% of relative standard deviation for all the pesticides. The multiresidue method for estimating pesticide residues employing GC-MS/MS technique will be useful for OP pesticide levels in large number of lanolin samples.

Determination of cholesterol oxides by gas chromatography-flame ionization detection/mass selective detection and their occurence in lanolin-containing cosmetics and ointments.

OBJECTIVE: Cholesterol oxides (COPs) are thought to be of toxicological relevance in cholesterol-containing foods. For cholesterol-containing cosmetics and the like, no information is available up to this date. Therefore, the first of two main aims of this study was to develop and validate a method for determining COPs in lanolin-containing cosmetics such as lipsticks and fatty creams as well as in nipple ointments. The second aim was to study the occurrence of COPs and their concentration levels in the respective product classes. METHODS: The procedure is based on a published method for food comprising some necessary modifications. Sample preparation consisted of transesterfication, solid-phase extraction and silylation of target compounds. Separation of the derivatized COPs and their quantification were performed with gas chromatography (GC) using a flame ionization detector (FID) or a mass spectrometer (MS). RESULTS: The successful validation and the trouble-free application during the market survey showed that the method was fit for purpose. Total COP levels found were in the low per cent range (up to 3%) and surprisingly high, being many orders of magnitude higher than those published for foods. CONCLUSION: To our knowledge, we present for the first time a method for the determination of COPs in non-food consumer products. Furthermore, our study demonstrates that lanolin-containing cosmetics may be an additional exogenous source of COPs. We further show evidence, that at least part of the COPs are already formed on the sheep's wool.

Oxysterols in cosmetics-Determination by planar solid phase extraction and gas chromatography-mass spectrometry.

Sterol oxidation products (SOPs) are linked to several toxicological effects. Therefore, investigation of potential dietary uptake sources particularly food of animal origin has been a key issue for these compounds. For the simultaneous determination of oxysterols from cholesterol, phytosterols, dihydrolanosterol and lanosterol in complex cosmetic matrices, planar solid phase extraction (pSPE) was applied as clean-up tool. SOPs were first separated from more non-polar and polar matrix constituents by normal phase thin-layer chromatography and then focussed into one target zone. Zone extraction was performed with the TLC-MS interface, followed by gas chromatography-mass spectrometry analysis. pSPE showed to be effective for cleaning up cosmetic samples as sample extracts were free of interferences, and gas chromatographic columns did not show any signs of overloading. Recoveries were between 86 and 113% with relative standard deviations of below 10% (n=6). Results of our market survey in 2016 showed that some cosmetics with ingredients of plant origin contained phytosterol oxidation products (POPs) in the low ppm range and therefore in line with levels reported for food. In lanolin containing products, total SOPs levels (cholesterol oxidation products (COPs), lanosterol oxidation products (LOPs), dihydrolanosterol oxidation products (DOPs)) being in the low percent range exceeded reported levels for food by several orders of magnitudes.

Mild soaps and radiotherapy: a survey of the UK public to identify brands of soap considered mild and analysis of these to ascertain suitability for recommendation in radiotherapy departments.

Cancer agencies recommend that patients use mild soap when undergoing external beam radiotherapy to minimise skin reactions. They define 'mild soap' as non-alkaline, lanolin free, unperfumed soap with a neutral pH. This study aimed to identify which soaps the UK public perceive as mild and ascertain if these were clinically mild and could potentially be recommended within radiotherapy departments. A survey of 237 participants identified eight top brands of mild soap, which were then tested for pH and analysed for potential irritants. All soaps were lanolin free and non-alkaline, with Simple and Johnson's the closest to pH 5.5. All contained fragrances except Simple and E45. Dove, Pears and Imperial Leather contained the highest concentration of fragrances. All soaps except E45 contained potential irritants. Only Simple and E45 fit the cancer agencies' definition of mild soap and could therefore be recommended for radiotherapy patients. Future research should identify current practices and recommendations in the UK as anecdotal evidence suggests large variations in skin care advice. Further scientific analysis could potentially identify cheaper brands that fit the definition of 'mild'. UK recommendations should be standardised and consistent with best practice to reduce skin reaction severity in radiotherapy patients.

Multiresidue determination of pesticides in lanolin using matrix solid-phase dispersion.

An efficient, fast, and accurate matrix solid-phase dispersion sample cleanup procedure was developed specifically for the determination of pesticide residues in lanolin. The scope of the method for organophosphorus, organochlorine, and pyrethroid insecticides is the same as that of official methods from various pharmacopeias. After lanolin dispersion on C18 bonded silica, pesticides are eluted with acetonitrile saturated with n-hexane. Recoveries ranged from 83 to 118% with RSD values of < 20% for most pesticides listed, in compliance with the requirements of European and U.S. pharmacopeias.

Acute allergic contact dermatitis of the lips from peppermint oil in a lip balm.

The etiology of cheilitis is often not readily apparent. We present a case series of four patients with allergic contact cheilitis (ACC) secondary to exposure to peppermint oil contained in a lip balm product. These patients developed eczematous dermatitis involving their lips and perioral skin. They were tested with the North American Contact Dermatitis Group standard series as well as with an expanded series of flavoring agents, sunscreens, plant and fragrance components, and their own products. The lip balm contained potential sensitizers such as propolis, lanolin, coconut oil, almond oil, peppermint oil, and vitamin E. Our patch-test results showed that peppermint oil was the most likely culprit in these patients' ACC. Peppermint oil is less commonly reported as causing ACC than are more common contactants such as balsam of Peru or nickel sulfate. However, with the widespread use of lip balms containing peppermint oil, more cases of peppermint oil-induced ACC may be expected.

[Analysis of constituents of ester-type gum bases used as natural food additives].

The differences in the constituents of ten ester-type gum bases used as natural food additives in Japan (urushi wax, carnauba wax, candelilla wax, rice bran wax, shellac wax, jojoba wax, bees wax, Japan wax, montan wax, and lanolin) were investigated. Several kinds of gum bases showed characteristic TLC patterns of lipids. In addition, compositions of fatty acid and alcohol moieties of esters in the gum bases were analyzed by GC/MS after methanolysis and hydrolysis, respectively. The results indicated that the varieties of fatty acids and alcohols and their compositions were characteristic for each gum base. These results will be useful for identification and discrimination of the ester-type gum bases.

Clean-up of a pesticide-lanolin mixture by gel permeation chromatography.

In this study, the efficiency of a clean-up method by gel permeation chromatography (GPC) for the separation of pesticides from lanolin is analyzed. The pesticides analyzed belong to two different families, organophosphorous and synthetic pyrethroids. Lanolin, a standard mixture of the pesticides, and a lanolin-pesticides mixture are injected in a GPC column. The recoveries and elution times from the GPC column of lanolin (by a gravimetric method) and pesticides (by gas chromatography-electron capture detector) are determined. From this column, a good separation of the lanolin-pesticides mixture is observed.

Simplified extraction and cleanup for multiresidue determination of pesticides in lanolin.

In the proposed method, a light petroleum solution of lanolin (wool fat) is adsorbed on diatomaceous earth in an Extrelut column, and the pesticides are eluted with acetonitrile saturated with light petroleum. After evaporation to a small volume, the extract is subjected to solid-phase extraction (SPE) on a C-18 column. The acetonitrile eluate is evaporated to dryness and the residue is taken up in light petroleum. Organophosphorus pesticides are determined by temperature-programmed gas chromatography (GC) on a wide-bore column using a flame photometric detector in the phosphorus mode. Organochlorine pesticides are determined after miniaturized Florisil cleanup by classic GC on an OV-17/QF-1 packed column, using an electron capture detector. This procedure is more rapid and straightforward than the time-consuming AOAC extraction method, 29.014. Cleanup was better and the results obtained were comparable. Recoveries for 13 organochlorine and organophosphorus pesticides, frequently found in lanolin, ranged from 80 to 90%.

An attempt to isolate and identify allergens in lanolin.

One sensitizer, a sterol, has previously been reported to be present in lanolin. In this study, a related substance, a sterol, with a molecular weight of 424 has been isolated. A few sensitive subjects did not react to this substance. Lanolin probably contains several sensitizers. Sensitization to lanolin in guinea pigs seems previously to have failed. In this study, a methanol extract of a lanolin preparation containing large amounts of sterols sensitized guinea pigs.

Lanolin of reduced sensitizing potential.

Confirmation has been obtained that reducing the content of natural free alcohols in lanolin to below 3%, particularly in the absence of detergent residues, reduces the incidence of positive patch test reactions amongst selected lanolin-sensitive skin patients by 99.3%. Only one reaction out of 149 subjects was recorded.