Analysis of preservatives and fragrances in topical medical devices: The need for more stringent regulation.

INTRODUCTION: Medical devices (MDs) have a long history of use, and come with regulatory frameworks to ensure user safety. Although topically applied MDs in the form of gels and creams might be used on damaged skin, their composition is often similar to that of cosmetic products applicable to intact skin, especially in terms of preservatives and fragrances. However, unlike cosmetics, these products are not subject to compound-specific restrictions when used in MDs. OBJECTIVE: This study aimed to identify and quantify preservatives and fragrances in topically applied MDs and assess their safety towards the Cosmetic Regulation (EC) 1223/2009. METHOD: Sixty-nine MDs available on the EU market were subjected to previously validated liquid chromatography tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) methods to identify and quantify occurring preservatives and fragrances. RESULTS: Findings revealed that 32% of the examined MDs did not provide comprehensive ingredient lists, leaving users uninformed about potential risks associated with product use. Furthermore, 30% of these MDs would not meet safety standards for cosmetic products and, most significantly, 13% of the analysed samples contained ingredients that are prohibited in leave-on cosmetics. CONCLUSION: Results highlight the pressing demand for more stringent requirements regarding the labelling and composition of MDs to enhance patient safety. Improved regulation and transparency can mitigate potential risks associated with the use of topically applied MDs.

Mass-Spectrometry-Based Research of Cosmetic Ingredients.

Cosmetic products are chemical substances or mixtures used on the skin, hair, nails, teeth, and the mucous membranes of the oral cavity, whose use is intended to clean, protect, correct body odor, perfume, keep in good condition, or change appearance. The analysis of cosmetic ingredients is often challenging because of their huge complexity and their adulteration. Among various analytical tools, mass spectrometry (MS) has been largely used for compound detection, ingredient screening, quality control, detection of product authenticity, and health risk evaluation. This work is focused on the MS applications in detecting and quantification of some common cosmetic ingredients, i.e., preservatives, dyes, heavy metals, allergens, and bioconjugates in various matrices (leave-on or rinse-off cosmetic products). As a global view, MS-based analysis of bioconjugates is a narrow field, and LC- and GC/GC×GC-MS are widely used for the investigation of preservatives, dyes, and fragrances, while inductively coupled plasma (ICP)-MS is ideal for comprehensive analysis of heavy metals. Ambient ionization approaches and advanced separation methods (i.e., convergence chromatography (UPC2)) coupled to MS have been proven to be an excellent choice for the analysis of scented allergens. At the same time, the current paper explores the challenges of MS-based analysis for cosmetic safety studies.

Macroevolution of floral scent chemistry across radiations of male euglossine bee-pollinated plantsMacroevolución de olores florales a través de radiaciones de plantas polinizadas por abejas euglosinas machosMacroevolução dos voláteis florais em radiações de plantas polinizadas por machos de abelhas Euglossini.

Floral volatiles play key roles as signaling agents that mediate interactions between plants and animals. Despite their importance, few studies have investigated broad patterns of volatile variation across groups of plants that share pollinators, particularly in a phylogenetic context. The "perfume flowers," Neotropical plant species exhibiting exclusive pollination by male euglossine bees in search of chemical rewards, present an intriguing system to investigate these patterns due to the unique function of their chemical phenotypes as both signaling agents and rewards. We leverage recently developed phylogenies and knowledge of biosynthesis, along with decades of chemical ecology research, to characterize axes of variation in the chemistry of perfume flowers, as well as understand their evolution at finer taxonomic scales. We detect pervasive chemical convergence, with many species across families exhibiting similar volatile phenotypes. Scent profiles of most species are dominated by compounds of either the phenylpropanoid or terpenoid biosynthesis pathways, while terpenoid compounds drive more subtle axes of variation. We find recapitulation of these patterns within two independent radiations of perfume flower orchids, in which we further detect evidence for the rapid evolution of divergent floral chemistries, consistent with the putative importance of scent in the process of adaptation and speciation.

To be or not to be fragrant: floral scent of some bat-pollinated cacti.

Floral scent is a key olfactory cue in both diurnal and nocturnal pollination systems. In the case of nocturnal systems, such as bat-pollinated flowers, odour seems to play a more important role than visual cues. Cactaceae include many bat-pollinated species; however, few studies have investigated the olfactory cues in this family. We analysed and compared the chemical composition of the floral bouquet of three chiropterophilous cactus species, among which are a pair of congeners that differ considerably in scent intensity. Our research presents novel findings regarding the floral scent chemistry of chiropterophilous cactus species. We documented the first case of a bat-pollinated cactus whose flowers lack perceptible floral scent and in which no volatile compounds were detected in our chemical analyses. Additionally, we provide a comprehensive analysis of the chemical composition of the floral bouquet of the other two bat-pollinated species, revealing a resemblance among closely related species within the same genus. We highlight the need for further studies using biotests to investigate the mechanisms through which bats find flowers lacking scent.

The Safety Assessment of Cosmetic Perfumes by Using In Chemico and In Vitro Methods in Combination with GC-MS/MS Analysis.

Animal testing has been prohibited for the safety assessment of cosmetic ingredients or finished products. Thus, alternative non-animal methods, followed by confirmatory clinical studies on human volunteers, should be used as the sole legally acceptable approach within the EU. The safety assessment of cosmetic products requires the involvement of multiple scientific disciplines, including analytical chemistry and biomedicine, as well as in chemico, in vitro and in silico toxicology. Recent data suggest that fragrance components may exert multiple adverse biological effects, e.g. cytotoxicity, skin sensitisation, (photo)genotoxicity, mutagenicity, reprotoxicity and endocrine disruption. Therefore, a pilot study was conducted with selected samples of fragrance-based products, such as deodorant, eau de toilette and eau de parfum, with the aim of integrating results from a number of alternative non-animal methods suitable for the detection of the following toxicological endpoints: cytotoxicity (with 3T3 Balb/c fibroblasts); skin sensitisation potential (in chemico method, DPRA); skin sensitisation potential (LuSens in vitro method, based on human keratinocytes); genotoxicity potential (in vitro Comet assay with 3T3 Balb/c cells); and endocrine disruption (in vitro YES/YAS assay). The presence of twenty-four specific known allergens in the products was determined by using GC-MS/MS. The strategies for estimation of the NOAEL of a mixture of allergens, which were proposed by the Scientific Committee on Consumer Products in their 'Opinion on Tea tree oil' document and by the Norwegian Food Safety Authority in their 'Risk Profile of Tea tree oil' report, were used as models for the NOAEL estimation of the mixtures of allergens that were identified in the individual samples tested in this study.

Hidden threat lurking in extensive hand hygiene during the Covid-19 pandemic: investigation of sensitizing molecules in gel products by hyphenated chromatography techniques.

During the Covid-19 pandemic, health agencies worldwide have recommended frequent handwashing and sanitizing. A variety of hand gel products were made available on the market, often with fragrances added to curtail the strong smell of alcohol. Commonly used Citrus fragrances contain volatile aroma constituents and non-volatile oxygen heterocyclic compounds (OHCs), consisting mostly of polymethoxyflavones, coumarins, and furocoumarins. The latter have long been investigated for their phototoxic properties, and their safety as cosmetic product ingredients has been debated recurrently. To this concern, twelve commercial Citrus-scented products were investigated in this study. An extraction method was optimized for thirty-seven OHC compounds, obtaining absolute mean recovery values in the 73.5-116% range with only few milliliters of solvent consumption. Analysis by ultra-high-pressure liquid chromatography with tandem mass spectrometry detection evidenced that three samples did not conform to the labeling requirements for fragrance allergens (coumarin) laid down by the European Union Regulation on Cosmetic Products. The total furocoumarin (FC) content of the samples investigated was in the 0.003-3.7ppm range, with some noteworthy exceptions. Specifically, in two samples, the total FCs were quantified as 89 and 219 ppm, thus exceeding the safe limits recommended up to a factor of 15. Finally, the consistency of the volatile fingerprint attained by gas chromatography allowed drawing conclusions on the authenticity of the Citrus fragrances labeled, and several products did not conform to the information reported on the label concerning the presence of essential oils. Besides the issue of product authenticity, analytical tools and regulatory actions for widespread testing of hand hygiene products are urgent, to protect consumers' health and safety.

Global distribution and ecological risk assessment of synthetic musks in the environment.

Synthetic musks, as an alternative product of natural musks, are widely used in almost all fragrances of consumer products, such as perfumes, cosmetics and detergents. During the past few decades, the production of synthetic musks has been increasing year by year, subsequently followed by large concern about their adverse effects on ecosystems and human beings. Until now, several studies have reviewed the latest development of analytical methods of synthetic musks in biological samples and cosmetics products, while there is still lack of a systematic analysis of their global distribution in different environmental media. Thus, this review summarizes the occurrence of synthetic musks in the environment including biota around the world and explores their global distribution patterns. The results show that galaxolide (HHCB), tonalide (AHTN), musk xylene (MX) and musk ketone (MK) are generally the most frequently detected synthetic musks in different samples with HHCB and AHTN being predominant. Higher concentrations of HHCB and AHTN are normally found in western countries compared to Asian countries, indicating more consumptions of these musks in western countries. The persistence, bioaccumulation and toxicity (PBT) of synthetic musks (mainly for polycyclic musks and nitro musks) are also discussed. The risk quotients (RQs) of HHCB, AHTN, MX and MK in most waters and sediments are below 0.1, reflecting a low risk to aqueous and sediment-dwelling species. In some sites, e.g., close to STPs, high risks (RQs>1) are characterized. Currently, limited data are available for macrocyclic musks and alicyclic musks in terms of either occurrence or PBT properties. More studies with an expanded scope of chemical type, geographical distribution and (synergic) toxicological effects especially from a long-term point of view are needed.

Non-species-specific pollen transfer and double-reward production in euglossine-pollinated Vanilla.

Commonly attributed to orchids, the pollen movement in Vanilla has been associated with food deception and specific plant-pollinator relationships. This study investigated the role of flower rewards and pollinator specificity in the pollen transfer of a widely distributed member to the euglossinophilous Vanilla clade, V. pompona Schiede using data collected from Brazilian populations. These included investigations on morphology, light microscopy and histochemistry, and analysis of flowers scent using GC-MS. The pollinators and the mechanisms of pollination were recorded through focal observations. The yellow flowers of V. pompona are fragrant and offer nectar as reward. The major volatile compound of the V. pompona scent, carvone oxide, shows convergent evolution in Eulaema-pollinated Angiosperms. The pollination system of V. pompona is not species-specific, but its flowers are strongly adapted to pollination by large Eulaema males. Pollination mechanism is based in a combination of perfume collection and nectar seeking. The dogma of a species-specific pollination system based on food deception in Vanilla has been broken with the increase in studies on this Pantropical orchid genus. Here, least three bee species and dual reward-offering are involved in pollen transfer in V. pompona. Visitation frequency of bees collecting perfumes, used in courtship by male euglossines, is higher than in searching for food, as short-lived young euglossine males seem to be more interested in sex than food. A pollination system based on offering both nectar and perfumes as resources is described for the first time in orchids.

[Simultaneous determination of 28 fragrance components in cosmetics by gas chromatography-tandem mass spectrometry].

With the increasing number of cosmetic products, their flavor and fragrance components are receiving greater and greater attention. Establishing an analytical method of determining these components in cosmetics is one of the most effective measures to eliminate consumers' concerns. In this study, a method for the simultaneous determination of 28 fragrance residues in cosmetics by gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed. The samples were extracted using methanol and those containing more oil and grease were purified using a neutral alumina solid-phase extraction column, whereas those with more complex compositions were purified by QuEChERS. The analytes in the samples were measured by GC-MS/MS, characterized using their retention times and characteristic ion pairs, and quantified with an external standard. The respective limits of detection (LODs, S/N=3) and quantification (LOQs, S/N>10) of the compounds were in the ranges 2-20 and 5-50 µg/kg. The linearities of the concentration curves of the 28 substances were good in the ranges 1-100, 2-200, 4-200, and 10-1000 µg/L, and the correlation coefficients of the quantitative ion pairs were >0.999. Twenty-eight fragrances were added to blank samples at spiked levels of 50-500 µg/kg, and the recoveries ranged from 71.3% to 120.4%, with RSDs of 1.5%-14.6%. The method could be applied in the determination of fragrances in cosmetics because it was simple, sensitive, and stable and could effectively exclude the interferences of complex matrices. The method was used to determine the fragrance components in 16 cosmetic products, and some fragrance components were detected in 12 samples. Increased attention should be paid to the safeties of fragrances and flavors used in cosmetics.

Lysmeral Exposure in Children and Adolescences Participating in the German Environmental Survey (2012-2015): Integrating Sex/Gender into Analysis.

Comprehensive consideration of the biological and social diversities of sex and gender as well as their interdependencies is mostly missing in human biomonitoring (HBM) studies. Using the INGER sex/gender concept as theoretical background, we analyzed differences in exposure to lysmeral, a compound commonly found as a fragrance in cosmetics, personal care, and household products, in 2294 children and adolescents in Germany using decision tree, regression, and mediation analysis. The variables "sex assigned at birth" and "age", as well as well as use of personal care products and fabric conditioner proved to have the highest explanatory value. Mediating effects of behaviour associated with societal gender expectations were observed, as the use of cosmetics correlated highly with lysmeral metabolites concentrations in girls between 6 and 17 years, with the strongest effect in adolescents between 14 and 17 years old. In the youngest age group (3-5 years) boys showed higher concentration of the metabolite tert-butylbenzoic acid (TBBA) compared to girls of the same age but only if TBBA urine concentrations were normalized on creatinine. Our study offers the first retrospective sex/gender assessment of HBM data. It demonstrates the possibilities to rethink and broaden sex/gender analysis in existing HBM-studies and highlights the need for inclusion of new sex/gender concepts in the design of new studies.

Screening of antimicrobials, fragrances, UV stabilizers, plasticizers and preservatives in sewage treatment plants (STPs) and their risk assessment in India.

Community/industrial wastewater is the prime source of anthropogenic chemicals, its treatment is often a daunting task and unaffordable for many countries. Emerging Contaminants (ECs) have been drained into wastewater after continuous use/misuse and Conventional treatments in STPs do not remove them completely. ECs including antimicrobial agents, synthetic musks, Benzotriazole UV stabilizers (BUVSs), plasticizers, and preservatives are frequently reported in environment, and cause health effects to non-target organisms. Monitoring of ECs is important to understand their status in aquatic environment. Hence, it was aimed to monitor ECs (n = 21) from 11 STPs in Tamil Nadu, India. The detection frequency of most of these analytes was >90%. Antimicrobials ranged from 247 to 22,714 ng/L and 11-14,369 ng/L in influents and effluents, respectively. The synthetic musks were in the order of Tonalide > Galaxolide > Musk Ketone. BUVSs ranged from 4 to 1632 ng/L (influents) and < LOD to 29,853 ng/L (effluents). Concentration of phthalates in influents and effluents were < LOD - 11,311 ng/L and < LOD - 17,618 ng/L, respectively. Parabens were found in the order of Prophyl > Methyl > Ethyl > Butyl in influents and Methyl > Prophyl > Butyl > Ethyl in effluents. Mass loads of ECs through STPs were found as antimicrobials > plasticizers > fragrances > BUVSs > Preservatives. This study reveals increasing usage of ECs and inadequate treatment processes at STPs in India. Also helps to adopt suitable treatment processes to remove ECs from wastewater and to reuse the wastewater.

An evaluation of qH NMR: A complementary approach to GC-FID for quantification of Thymol and trans-Anethole in essential oils and supplements.

Sweet fennel (Foeniculum vulgare Mill. var. dulce) and thyme (Zataria multiflora Boiss.) are regarded as the important supplies for pharmaceutical, food, cosmetic, and perfume industries. The major components trans-anethole and thymol are represented in fennel and thyme, respectively. The essential oils (EOs) content and the value of their related constituents should be given in strict quality control due to the storage conditions, source, and adulterations. In this study, we compared the validation of quantitative 1H NMR (qH NMR) method with the gas chromatography with flame ionization detection (GC-FID) to quantify the trans-anethole and thymol in fennel and thyme EOs and their related supplements. The current results showed that the quantification of trans-anethole and thymol by qH NMR method was successfully achieved from their EOs and supplements. All the validation parameters including linearity, robustness, repeatability, and stability were authenticated for thymol and trans-anethole quantification. Similar results were obtained in both qH NMR and conventional GC-FID methods. Therefore, according to the measured values, the qH NMR method was adequate to determine the constituents of the EOs, with the results being roughly comparable to those obtained by GC-FID, with the advantage of being simple, repeatable, rapid (8-10 min, while for GC-FID 55 min) and essential for quality control of commercial samples.

Adsorption of pesticides and personal care products on pristine and weathered microplastics in the marine environment. Comparison between bio-based and conventional plastics.

The hydrophobicity of persistent organic pollutants (POPs) makes them adsorb on microplastics in the marine environment, affecting their distribution, persistence, or their transfer to the trophic chain. Fragrances and non-polar pesticides can be adsorbed by microplastics in the marine environment because of their physico-chemical characteristics. In this work, the adsorption of two pesticides (α-endosulfan and chlorpyrifos) and 6 musk fragrances (musk xylene, musk ketone, musk moskene, galaxolide, tonalide, and celestolide) on polyamide (PA6) (a petroleum based polymer) and on polyhydroxybutyrate (PHB) (biopolymer) in seawater was studied, considering also the effect of water temperature and plastic weathering. Results show higher adsorption of the selected pollutants for PHB than PA, being PA more affected by the water temperature and the plastic weathering. The highest percentage of adsorption was achieved in most cases at 24 h. In addition, this process was irreversible, as it showed the leaching assays. Besides, this work revealed that plastics mitigate the degradation of α-endosulfan in aquatic media (hydrolysis), showing that plastics can act as inhibitors of degradation of POPs, increasing its persistence in the environment.

Agarwood-The Fragrant Molecules of a Wounded Tree.

Agarwood, popularly known as oudh or gaharu, is a fragrant resinous wood of high commercial value, traded worldwide and primarily used for its distinctive fragrance in incense, perfumes, and medicine. This fragrant wood is created when Aquilaria trees are wounded and infected by fungi, producing resin as a defense mechanism. The depletion of natural agarwood caused by overharvesting amidst increasing demand has caused this fragrant defensive resin of endangered Aquilaria to become a rare and valuable commodity. Given that instances of natural infection are quite low, artificial induction, including biological inoculation, is being conducted to induce agarwood formation. A long-term investigation could unravel insights contributing toward Aquilaria being sustainably cultivated. This review will look at the different methods of induction, including physical, chemical, and biological, and compare the production, yield, and quality of such treatments with naturally formed agarwood. Pharmaceutical properties and medicinal benefits of fragrance-associated compounds such as chromones and terpenoids are also discussed.

Obtaining Aromatic Extracts from Portuguese Thymus mastichina L. by Hydrodistillation and Supercritical Fluid Extraction with CO2 as Potential Flavouring Additives for Food Applications.

Humans often respond to sensory impulses provided by aromas, and current trends have generated interest in natural sources of fragrances rather than the commonly used synthetic additives. For the first time, the resulting aroma of a selected culture of Thymus mastichina L. was studied as a potential food ingredient. In this context, dried (DR) and fresh (FR) samples were submitted to carbon dioxide (CO2) supercritical extraction (SFE) and hydrodistillation (HD) methods. The extracts were characterised according to their volatile composition by GC-MS, cytotoxicity against a non-tumour cell culture, and sensory attributes (odour threshold and olfactive descriptors). The most abundant aromas were quantified, and the analysis performed by GC-MS revealed an abundance of terpenoids such as thymol chemotype, followed by the precursors α-terpinene and p-cymene. DR and FR extracts (EX) obtained from SFE-CO2 show the highest content of thymol, achieving 52.7% and 72.5% of the isolated volatile fraction. The DR essential oil (EO) contained the highest amount of terpenoids, but it was also the most cytotoxic extract. In contrast, SFE-CO2 products showed the lowest cytotoxic potential. Regarding FR-OE, it had the lowest extraction yield and composition in aroma volatiles. Additionally, all samples were described as having green, fresh and floral sensory notes, with no significant statistical differences regarding the odour detection threshold (ODT) values. Finally, FR-EX of T. mastichina obtained by SFE-CO2 presented the most promising results regarding food application.

Supercritical CO2 Extraction of Narcissus poeticus L. Flowers for the Isolation of Volatile Fragrance Compounds.

The flowers of Narcissus poeticus are used for the isolation of valuable fragrance substances. So far, as the majority of these substances consist of volatile and sensitive to heat compounds, there is a need of developing effective methods for their recovery. In this study, freeze-dried N. poeticus inflorescences were extracted with pure supercritical CO2 (SFE-CO2) and its mixture with 5% co-solvent ethanol (EtOH) at 40 °C. Extract yields varied from 1.63% (12 MPa) to 3.12% (48 MPa, 5% EtOH). In total, 116 volatile compounds were identified by GC-TOF/MS in the extracts, which were divided into 20 different groups. Benzyl benzoate (9.44-10.22%), benzyl linoleate (1.72-2.17%) and benzyl alcohol (0.18-1.00%) were the major volatiles among aromatic compounds. The amount of the recovered benzyl benzoate in N. poeticus SFE-CO2 extracts varied from 58.98 ± 2.61 (24 MPa) to 91.52 ± 1.36 (48 MPa) mg/kg plant dry weight (pdw). α-Terpineol dominated among oxygenated monoterpenes (1.08-3.42%); its yield was from 9.25 ± 0.63 (12 MPa) to 29.88 ± 1.25 (48 MPa/EtOH) mg/kg pdw. Limonene was the major monoterpene hydrocarbon; (3E)-hexenol and heneicosanol dominated among alcohols and phenols; dihydroactinidiolide and 4,8,12,16-tetramethyl heptadecan-4-olide were the most abundant lactones; heptanal, nonanal, (2E,4E)-decadienal and octadecanal were the most abundant aldehydes. The most important prenol lipids were triterpenoid squalene, from 0.86 ± 0.10 (24 MPa) to 7.73 ± 0.18 (48 MPa/EtOH) mg/kg pdw and D-α-tocopherol, from 1.20 ± 0.04 (12 MPa) to 15.39 ± 0.31 (48 MPa/EtOH) mg/kg pdw. Aliphatic hydrocarbons (waxes) constituted the main part (41.47 to 54.93%) in the extracts; while in case of a 5% EtOH the percentage of alkanes was the lowest. The fraction of waxes may be removed for the separation of higher value fragrance materials. In general, the results obtained are promising for a wider application of SFE-CO2 for the recovery of fragrance substances from N. poeticus flowers.

Immobilization of phosphonium-based ionic liquid stationary phases extends their operative range to routine applications in the flavor, fragrance and natural product fields.

Phosphonium-based ionic liquids (ILs) have proven to be successful stationary phases (SPs) for gas chromatography (GC) in several fields of application because of their unique selectivity and good chromatographic properties. This study focuses on the use of two ILs as GC SPs that are based on the phosphonium derivatives trihexyl(tetradecyl)phosphonium chloride ([P66614+] [Cl-]), and trihexyl(tetradecyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide ([P66614+][NTf2-]), which have previously been shown to be complementary in terms of chromatographic selectivity and retention. Their application in routine analysis has been limited by their lower maximum allowable operating temperatures (MAOT) (200 °C for the [P66614+][Cl-] IL and 180 °C for [P66614+][NTf2-]), which restricts their use to samples that consist of analytes with relatively high volatility. A previous study carried out in the Authors' laboratory focused on extending the use of the [P66614+][Cl-] IL SP to the analysis of samples with analytes of medium-to-low volatility by optimizing column characteristics and operative conditions. This study addresses the immobilization of both the [P66614+][Cl-] and [P66614+][NTf2-] ILs to the inner wall of fused silica columns to increase their MAOT under soft and hard reaction conditions. The resulting MAOT depended on more or less drastic immobilization conditions, and reached 220 °C for soft immobilization (So-Im) and 240 °C for hard immobilization (Ha-Im) in the [P66614+][Cl-] IL columns, and 200 °C for So-Im and 220° for Ha-Im in columns coated with the [P66614+] [NTf2-] IL. The influence of immobilization on the separation power and performance of all the columns has been evaluated using i) the Grob test, ii) a model mixture of 41 compounds of different polarity, structure, and with different organic functional groups representative of the flavor and fragrance field, iii) a standard mixture of 37 fatty acid methyl esters, iv) the peppermint essential oil, v) two mixtures of sesquiterpenic alcohols (farnesols and santalols), and vi) a standard mixture of 16 pesticides. These test samples were also used to demonstrate the complementarity of the two phosphonium-based IL SPs in terms of selectivity and retention.

Country-Specific Environmental Risks of Fragrance Encapsulates Used in Laundry Care Products.

Fragrance encapsulates (FEs) are designed to deliver fragrance components, notably in laundry care products. They are made of thermoset polymeric shells surrounding the fragrance content. These materials enter the environment mainly during laundry washing, but little is known about their distribution in and impact on the environment. The aim of the present study was to estimate the environmental concentrations of FE shells in freshwater, sediment, and soil compartments for 34 selected countries and to compare them with ecotoxicological effects. Probabilistic material flow analysis was used to estimate worst-case predicted environmental concentrations (PECs). The lowest freshwater PEC was predicted for Finland (0.00011 µg/L) and the highest for Belgium (0.13 µg/L). Accumulation of FE shells between 2010 and 2019 was considered for sediments and sludge-treated soils. The PECs in sediments ranged from 3.0 µg/kg (Finland) to 3400 µg/kg (Belgium). For sludge-treated soil, the concentration was estimated to be between 0 (Malta and Switzerland) and 3600 µg/kg (Vietnam). Ecotoxicological tests showed no effects for FE shells at any tested concentration (up to 2700 µg/L freshwater, 5400 µg/kg sediment, and 9100 µg/kg soil), thus not allowing derivation of a predicted-no-effect concentration (PNEC). Therefore, to characterize the environmental risks, the PEC values were compared with highest-observed-no-effect concentrations (HONECs) derived from ecotoxicological tests. The PEC/HONEC ratios were 9.3 × 10-6 , 0.13, and 0.04 for surface waters, sediments, and sludge-treated soils, respectively, which are much below 1, suggesting no environmental risk. Because the PEC values constitute an upper boundary (no fate considered) and the HONEC values represent a lower boundary (actual PNEC values based on NOECs will be higher), the current risk estimation can be considered a precautionary worst-case assessment. Environ Toxicol Chem 2022;41:905-916. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Time trend of the exposure to geraniol in 24-h urine samples derived from the German Environmental Specimen Bank from 2004 to 2018.

Geraniol (trans-3,7-dimethyl-2,6-octadiene-1-ol) is an acyclic isoprenoid monoterpene with a widespread use as fragrance in consumer products, agrochemicals and pharmaceuticals. The class of terpene chemicals has been associated with varying sensitizing potencies. A recently developed sensitive LC- MS/MS method for the analysis of geraniol metabolites was further improved and validated for the two metabolites, 8-carboxygeraniol and Hildebrandt acid. The successfully validated method was applied to 250 urine samples derived from the Environmental Specimen Bank (ESB) collected between 2004 and 2018. Both metabolites of this allergen of special concern were quantified in all urine samples of this study. Correlation analysis revealed that 8-carboxygeraniol appears to be the sole specific biomarker in urine for geraniol exposure. Overall, the excreted amounts of 8-carboxygeraniol remained unchanged in urine samples collected from 2004 to 2018. However, a significantly higher 8-carboxygeraniol excretion per 24 h was observed in females compared to males across the sampling years from 2004 to 2012. This trend equalized in the years 2015 and 2018. We could demonstrate that 8-carboxygeraniol may be a suited biomarker for assessing the geraniol exposure in the general population. Regardless of the fact that additional, preferably population representative studies combining HBM and health examination were helpful to further elucidate the risks of a geraniol exposure, the current study adds important data for identifying time trends and body burden of geraniol in the environment and shows the ubiquitous exposure towards mixtures of sensitizing chemicals.

Analysis of Fragrance Allergens in Personal Care Products, Toys, and Water Samples: A Review.

Fragrance allergens (FAs) refer to these volatile or semi-volatile fragrance compounds that can cause irritation and negative reactions. A large number of emerging FAs are widely used in household goods, and cause contact allergy or allergic contact dermatitis in eczema population and the general population. It shows an increasing prevalence and is regarded as a concern to public health. Recently, more and more studies have focused on the analytical methods of FAs in a variety of samples with different matrixes. Therefore, a systematic and comprehensive overview of recent progress of analysis of FAs in various samples is needed. In this review, the physical and chemical properties, applications, hazards, and the recent advances of sample preparation and determination methods of common FAs in personal care products, toys, and water samples are systematically and comprehensively summarized. Meanwhile, this review also discusses the advantages and limitations of different sample pretreatment and detection methods, thus offering a deep-going discussion of the development and future trends in this area.