The fragrant terpenes limonene and linalool can form skin sensitizing hydroperoxides upon prolonged exposure to air. Recently, high frequencies of positive patch tests to oxidized linalool and limonene were reported from multiple dermatological centres. However, there is a lack of data indicating potential sources of consumer exposure to sensitizing doses of terpene hydroperoxides which explains this frequent contact allergy. Within the IDEA project (International Dialogue for the Evaluation of Allergens; http://ideaproject.info/), a taskforce was formed to drive analytical method development and evaluation. In an inter‐laboratory study in five laboratories, a method based on hydroperoxide reduction combined with GC–MS was tested for reproducibility. Blinded samples of commercial fine fragrances were spiked with four different hydroperoxides. In samples spiked with 100–200 μg/ml, an average recovery of 86–105% with a relative standard deviation between laboratories of 7.4–22% was found. In samples spiked with 20–50 μg/ml, the recovery was 85–91%. The reduction approach offers a transferable and reproducible method to indirectly detect low levels of hydroperoxides, at least in fine fragrances. Ideally, one would prefer to directly detect the parent hydroperoxide. Therefore the same samples were further tested with three LC‐based methods directly detecting the parent hydroperoxide. LC coupled to chemiluminescence, LC‐Q‐TOF‐MS or LC‐orbitrap‐MS were used. Results indicate that with specific gradients a separation of the four analytes and quantification in the fragrance matrix can be achieved. Results of this method evaluation study present a toolbox of methods to detect terpene hydroperoxides to further investigate consumer exposure.

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Two high‐resolution mass spectrometers (HRMS) with different analyzer technology, Orbitrap and hybrid quadrupole time‐of‐flight (QTOF), were compared with a low‐resolution mass spectrometer, quadrupole, to analyse a set of 35 difficult allergens. These difficult allergens are commonly coeluted fragrance allergens with matrix compounds, using standard gas chromatography‐mass spectrometer conditions, from the extended list of the Scientific Committee on Consumer Safety (SCCS). Although the fundamental role of chromatographic separation has been demonstrated many times, the aim of this work is to demonstrate the benefits of high‐resolution. The added value of high‐resolution was illustrated in both a qualitative and a quantitative way. For qualitative aspect, the high resolution extracted ion signals of these two detectors were compared with the low‐resolution extracted ion signals. About 50% of the coeluted cases observed with the low‐resolution detector are easily resolved by the two high‐resolution detectors. For the quantitative aspect, an accuracy profile methodology and a performance metric were used to propose an overall evaluation. The Orbitrap mass spectrometer demonstrated a better overall performance, while the QTOF presented similar or even lower quantification performances than the quadrupole on the set of analysed fragrances.

Furocoumarins are secondary metabolites that occur in various plant species used as ingredients in fragrances and cosmetics. Those compounds have received an increased interest in those matrices since they are known to induce photosensitization and to have potential carcinogenic, mutagenic and reprotoxic effects. To date, there are no restricted limits regarding these compounds; however, some committees proposed following seven targeted compounds at low level concentration in finished cosmetic products (≤1 mg/l). This implies the need for a robust and specific analytical method to control and determine their concentrations in essential oils or more complex matrices such as fragrances. An innovative RP‐HPLC high‐resolution/accurate‐mass MS method based on Orbitrap technology was developed to quantify seven furocoumarins in fragrances in the range 0.01–1 mg/l. This method was developed and validated according to accuracy profile methodology. Accurate mass and high resolution provides a robust and highly specific approach to quantify the compounds and minimize tedious sample preparation. The method was finally used to quantify more than 50 perfumes (eaux de toilette, eaux de parfum, extraits). Copyright © 2014 John Wiley & Sons, Ltd.

Mixed chlorobromoanisoles have recently been recognized as new potential odorous compounds in tap water. The odour threshold concentrations (OTCs) of these compounds are close to the sub ng/L (ppt) and associated descriptors are "earthy, musty, rubber". During a "swampy, musty" episode in water of the Norrtälje district (Sweden), 2,4,6-mixed chlorobromoanisoles and their phenolic precursors were identified. These compounds were synthesised in order to quantify them in different types of waters, Samplings were performed during two different seasons. Results show that whatever the season, mixed haloanisoles and their precursors were present. Chlorination, biofilm activity and residence time in the distribution system seem to be critical factors for the appearance of such compounds.

The fragrant terpenes limonene and linalool can form skin‐sensitizing hydroperoxides (HPs) upon prolonged exposure to air. Sources of exposure of consumers to sensitizing doses of HPs have not been identified, and it is not clear whether fragranced products are a relevant source. Previously this question was addressed via analytical studies on fine fragrances; however, linalool and limonene are widely used in different consumer products, especially in other leave‐on toiletries. Hence, analytical methods also need to be able to detect potential HPs in more complex consumer product matrices. Here we applied different simple extraction methods and a toolbox of analytical methods to creams and lotions. Blinded samples of a commercial skin cream and a body lotion were spiked with four different HPs at different doses. Five laboratories analysed the samples with a method based on HP reduction in the sample, followed by Extrelut® NT extraction and GC‐MS to quantify the formed alcohols. This method found an average recovery of spiked levels of 80–105%, with a relative standard deviation between laboratories of 11–25% in samples spiked with 100–200 μg g−1. Quantification was also possible in samples spiked with 20–50 μg mL−1, with a relative standard deviation between laboratories of 11–38%. Thus, this method can indirectly detect low levels of HPs in complex bases. In parallel, the same samples were analysed with three LC‐based methods directly detecting the parent HPs: LC coupled with chemiluminescence, LC‐Q‐TOF‐MS, and LC‐orbitrap‐MS. On average, the different analytes were detected with a recovery of 80–143%. No HPs were detected in the non‐spiked products, despite the fact that they do contain linalool and limonene. Results of these studies indicate that consumer exposure can now be studied routinely in different product types as the required methods are ready for roll‐out.

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Lyon, France has the opportunity to distribute in abundance a groundwater resource with a good quality for drinking water. However, the length and the complexity of the distribution network can lead to consumer complaints in some areas of the water distribution system. In order to improve the organoleptic quality of distributed water, the water supplier wants to get a better understanding of potential taste and odour formation and to succeed in controlling it. Since 2006, activities have been taken with targeted analyses and sensory evaluation of water, taking into account both the consumers' private networks and the citywide distribution network. The first results were focused on the occurrence of bromophenols along the water distribution system, the understanding of the mechanisms of formation of such compounds, as well as their incidence on taste-and-odour events at the consumer's home.