A multi-platform approach for the comprehensive analysis of per- and polyfluoroalkyl substances (PFAS) and fluorine mass balance in commercial ski wax products.

The unique properties of per- and polyfluoroalkyl substances (PFAS) have led to their extensive use in consumer products, including ski wax. Based on the risks associated with PFAS, and to align with PFAS regulations, the international ski federation (FIS) implemented a ban on products containing "C8 fluorocarbons/perfluorooctanoate (PFOA)" at all FIS events from the 2021/2022 season, leading manufactures to shift their formulations towards short-chain PFAS chemistries. To date, most studies characterising PFAS in ski waxes have measured a suite of individual substances using targeted analytical approaches. However, the fraction of total fluorine (TF) in the wax accounted for by these substances remains unclear. In this study, we sought to address this question by applying a multi-platform, fluorine mass balance approach to a total of 10 commercially available ski wax products. Analysis of TF by combustion ion chromatography (CIC) revealed concentrations of 1040-51700 µg F g-1 for the different fluorinated waxes. In comparison, extractable organic fluorine (EOF) determined in methanol extracts by CIC (and later confirmed by inductively-coupled plasma-mass spectrometry and 19F- nuclear magnetic resonance spectroscopy) ranged from 92 to 3160 µg g-1, accounting for only 3-8.8 % of total fluorine (TF). Further characterisation of extracts by cyclic ion mobility-mass spectrometry (IMS) revealed 15 individual PFAS with perfluoroalkyl carboxylic acid concentrations up to 33 µg F g-1, and 3 products exceeding the regulatory limit for PFOA (0.025 µg g-1) by a factor of up to 100. The sum of all PFAS accounted for only 0.01-1.0 % of EOF, implying a high percentage of unidentified PFAS, thus, pyrolysis gas chromatography-mass spectrometry was used to provide evidence of the nature of the non-extractable fluorine present in the ski wax products.

Identification and quantification of fluorinated polymers in consumer products by combustion ion chromatography and pyrolysis-gas chromatography-mass spectrometry.

Total fluorine was determined in 45 consumer product samples from the Swedish market which were either suspected or known to contain fluorinated polymers. Product categories included cookware (70-550 000 ppm F), textiles (10-1600 ppm F), electronics (20-2100 ppm F), and personal care products (10-630 000 ppm F). To confirm that the fluorine was organic in nature, and deduce structure, a qualitative pyrolysis-gas chromatography-mass spectrometry (pyr-GC/MS) method was validated using a suite of reference materials. When applied to samples with unknown PFAS content, the method was successful at identifying polytetrafluoroethylene (PTFE) in cookware, dental products, and electronics at concentrations as low as 0.1-0.2 wt%. It was also possible to distinguish between 3 different side-chain fluorinated polymers in textiles. Several products appeared to contain high levels of inorganic fluorine. This is one of the few studies to quantify fluorine in a wide range of consumer plastics and provides important data on the concentration of fluorine in materials which may be intended for recycling, along with insights into the application of pyr-GC/MS for structural elucidation of fluorinated polymers in consumer products.

3D Molecular Imaging of Stratum Corneum by Mass Spectrometry Suggests Distinct Distribution of Cholesteryl Esters Compared to Other Skin Lipids.

The crucial barrier properties of the stratum corneum (SC) depend critically on the design and integrity of its layered molecular structure. However, analysis methods capable of spatially resolved molecular characterization of the SC are scarce and fraught with severe limitations, e.g., regarding molecular specificity or spatial resolution. Here, we used 3D time-of-flight secondary ion mass spectrometry to characterize the spatial distribution of skin lipids in corneocyte multilayer squams obtained by tape stripping. Depth profiles of specific skin lipids display an oscillatory behavior that is consistent with successive monitoring of individual lipid and corneocyte layers of the SC structure. Whereas the most common skin lipids, i.e., ceramides, C24:0 and C26:0 fatty acids and cholesteryl sulfate, are similarly organized, a distinct 3D distribution was observed for cholesteryl oleate, suggesting a different localization of cholesteryl esters compared to the lipid matrix separating the corneocyte layers. The possibility to monitor the composition and spatial distribution of endogenous lipids as well as active drug and cosmetic substances in individual lipid and corneocyte layers has the potential to provide important contributions to the basic understanding of barrier function and penetration in the SC.

A Curly Q: Is Frizz a Matter of Friction?

The oft discussed and fretted over environmental influences on hair have led to a popular consensus which suggests that elevated temperature and humidity lead to frizzier, wilder hair. However, few attempts at actually quantifying these effects have been made. Although frizziness is usually perceived visually, here the influence of variations in temperature and humidity on the tactile perception and friction of curly and straight hair were investigated. It is shown that changes in humidity may disproportionately affect perceived frizziness of curly hair by touch due to concurrent changes in the tactile friction.

The finishing touches: the role of friction and roughness in haptic perception of surface coatings.

Humans are extraordinarily skilled in the tactile evaluation of, and differentiation between, surfaces. The chemical and mechanical properties of these surfaces are translated into tactile signals during haptic exploration by mechanoreceptors in our skin, which are specialized to respond to different types of temporal and mechanical stimulation. Describing the effects of measurable physical characteristics on the human response to tactile exploration of surfaces is of great interest to manufacturers of household materials so that the haptic experience can be considered during design, product development and quality control. In this study, methods from psychophysics and materials science are combined to advance current understanding of which physical properties affect tactile perception of a range of furniture surfaces, i.e., foils and coatings, thus creating a tactile map of the furniture product landscape. Participants' responses in a similarity scaling task were analyzed using INDSCAL from which three haptic dimensions were identified. Results show that specific roughness parameters, tactile friction and vibrational information, as characterized by a stylus profilometer, a Forceboard, and a biomimetic synthetic finger, are important for tactile differentiation and preferences of these surface treatments. The obtained dimensions are described as distinct combinations of the surface properties characterized, rather than as 'roughness' or 'friction' independently. Preferences by touch were related to the roughness, friction and thermal properties of the surfaces. The results both complement and advance current understanding of how roughness and friction relate to tactile perception of surfaces.

Imaging the distribution of skin lipids and topically applied compounds in human skin using mass spectrometry.

The barrier functions of skin against water loss, microbial invasion and penetration of xenobiotics rely, in part, on the spatial distribution of the biomolecular constituents in the skin structure, particularly its horny layer (stratum corneum). However, all skin layers are important to describe normal and dysfunctional skin conditions, and to develop adapted therapies or skin care products. In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with scanning electron microscopy (SEM) was used to image the spatial distribution of a variety of molecular species, from stratum corneum down to dermis, in cross-section samples of human abdominal skin. The results demonstrate the expected localization of ceramide and saturated long-chain fatty acids in stratum corneum (SC) and cholesterol sulfate in the upper part of the viable epidermis. The localization of exogenous compounds is demonstrated by the detection and imaging of carvacrol (a constituent of oregano or thyme essential oil) and ceramide, after topical application onto ex vivo human skin. Carvacrol showed pronounced accumulation to triglyceride-containing structures in the deeper parts of dermis. In contrast, the exogenous ceramide was found to be localized in SC. Furthermore, the complementary character of this approach with classical ex vivo skin absorption analysis methods is demonstrated.

Mechanisms of tactile sensory deterioration amongst the elderly.

It is known that roughness-smoothness, hardness-softness, stickiness-slipperiness and warm-cold are predominant perceptual dimensions in macro-, micro- and nano- texture perception. However, it is not clear to what extent active tactile texture discrimination remains intact with age. The general decrease in tactile ability induces physical and emotional dysfunction in elderly, and has increasing significance for an aging population. We report a method to quantify tactile acuity based on blinded active exploration of systematically varying micro-textured surfaces and a same-different paradigm. It reveals that elderly participants show significantly reduced fine texture discrimination ability. The elderly group also displays statistically lower finger friction coefficient, moisture and elasticity, suggesting a link. However, a subpopulation of the elderly retains discrimination ability irrespective of cutaneous condition and this can be related to a higher density of somatosensory receptors on the finger pads. Skin tribology is thus not the primary reason for decline of tactile discrimination with age. The remediation of cutaneous properties through rehydration, however leads to a significantly improved tactile acuity. This indicates unambiguously that neurological tactile loss can be temporarily compensated by restoring the cutaneous contact mechanics. Such mechanical restoration of tactile ability has the potential to increase the quality of life in elderly.

Feeling small: exploring the tactile perception limits.

The human finger is exquisitely sensitive in perceiving different materials, but the question remains as to what length scales are capable of being distinguished in active touch. We combine material science with psychophysics to manufacture and haptically explore a series of topographically patterned surfaces of controlled wavelength, but identical chemistry. Strain-induced surface wrinkling and subsequent templating produced 16 surfaces with wrinkle wavelengths ranging from 300 nm to 90 µm and amplitudes between 7 nm and 4.5 µm. Perceived similarities of these surfaces (and two blanks) were pairwise scaled by participants, and interdistances among all stimuli were determined by individual differences scaling (INDSCAL). The tactile space thus generated and its two perceptual dimensions were directly linked to surface physical properties - the finger friction coefficient and the wrinkle wavelength. Finally, the lowest amplitude of the wrinkles so distinguished was approximately 10 nm, demonstrating that human tactile discrimination extends to the nanoscale.

Robust hydrophobic surfaces displaying different surface roughness scales while maintaining the same wettability.

A range of surfaces coated with spherical silica particles, covering the size range from nanometer to micrometer, have been produced using Langmuir-Blodgett (LB) deposition. The particles were characterized both in suspension and in the Langmuir trough to optimize the surface preparation procedure. By limiting the particle aggregation and surface layer failures during the preparation steps, well-defined monolayers with a close-packed structure have been obtained for all particle sizes. Thus, this procedure led to structured surfaces with a characteristic variation in the amplitude and spatial roughness parameters. In order to obtain robust surfaces, a sintering protocol and an AFM-based wear test to determine the stability of the deposited surface layer were employed. Hydrophobization of the LB films followed by water contact angle measurements showed, for all tested particle sizes, the same increase in contact angle compared to the contact angle of a flat hydrophobic surface. This indicates nearly hexagonal packing and gives evidence for nearly complete surface wetting of the surface features.