Cosmetic UV Filters Research Articles

Portable Voltammetry: A Rapid and Efficient Technique for Determining UV Filters in Cosmetics: A Comparative Study with HPLC-PDA and HPLC-MS/MS.

This study addresses the widespread use of UV filters (UVFs) in cosmetic and solar products due to the negative effects of UV radiation, particularly in relation to melanoma risk. While these filters offer protection, their extensive application raises concerns about their environmental and health impacts. Organic UVFs, in particular, have been associated with endocrine disruption in aquatic species and coral reef damage. To mitigate these concerns, regulatory limits have been imposed on certain UVFs. Current analytical techniques for UVF determination, such as HPLC-PDA and HPLC-MS/MS, offer high accuracy but are expensive and lack on-site monitoring capabilities. In response, this research aims to develop a rapid and cost-effective method, utilizing voltammetry for organic UVF quantification in complex matrices like sunscreens. Additionally, HPLC-PDA and HPLC-MS/MS are employed for electrochemical methods and device validation. This approach not only addresses the need for efficient UVF analysis but also provides a basis for regulatory compliance and environmental stewardship in the cosmetics industry.

Tailoring Bandgap and Photocatalytic Performance of Designed Zinc Oxide Platelets by Cobalt Doping

AbstractPlatelet‐shaped zinc oxide (ZnO) particles exhibit certain advantages compared to conventional micron and nano forms. Their superior surface coverage and excellent optical properties make these particles very attractive as UV filters in cosmetics and personal care applications. Although ZnO is non‐toxic, it exhibits photocatalytic activity (PCA), which increases when the size of particles approaches the nanoscale. High PCA of mineral/inorganic filters is not desired in cosmetics and personal care applications. Therefore, it is essential to develop strategies to reduce PCA of such materials under UV exposure. Accordingly, the research objective of this study is to develop an understanding of the effects of Co‐doping on the optoelectronic and crystal structure of platelet shaped ZnO particles with Zn1‐xMxO stoichiometry (x=0‐4 wt % cobalt). XRD‐based Rietveld refinement and WD‐XRF reveal that Co was successfully doped into the ZnO lattice. SEM and particle size analyses confirmed that the shape and size of the designed ZnO platelets did not change significantly after doping. ~85 % reduction in PCA has was achieved by 3 wt % Co doping which was attributed to reduced OH and O2 free radical concentration. These results clearly show that Co‐doping can be used to effectively tailor the bandgap and optical properties of the designed ZnO particles.

Cosmetic UV filters in the environment-state of the art in EU regulations, science and possible knowledge gaps.

The aim of this work was to review the principals of environmental hazard and risk assessment (ERA) of cosmetic UV filters registered under EU REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals). Furthermore, effects as obtained from non-standardized testing methods and organisms from scientific literature were compared against the predicted no effect concentrations (PNECs) as derived based on standardized test methods for the various environmental compartments under REACH. The REACH dossiers at the ECHA webpage were screened for available information related to basic physico-chemical data (i.e. water solubility, octanol-water partitioning coefficient), PNECs and associated data (data basis, assessment factors (AFs)). Scientific literature was screened for available ecotoxicity data and the adverse effect levels were compared against the derived PNECs under REACH. Current approaches for environmental risk assessments of UV filters were evaluated for its applicability for a direct release scenario. Under REACH, PNECs were derived for all hazardous UV filters. Although, PNECs were often derived for various environmental compartments (i.e. freshwater, marine water, sediment, soil), results from literature focused on aquatic data. Effects as observed within scientific literature matches in principle with the hazardous profile of the UV filters. Effects levels both on the acute and the chronic toxicity as retrieved from the non-standardized test organisms (literature) were above the derived PNECs under REACH. Currently, ERAs performed for cosmetic UV filters under REACH are solely tonnage driven and thus do not fully capture the use in sunscreens and associated leisure activities. Existing EU REACH regulation is considered as sufficient to evaluate the environmental safety of UV filters used in sunscreens. To cover the direct release of UV filters due to various leisure activities into the aquatic freshwater and marine environment, an additional application-based ERA is considered necessary.

Insights into manganese(VII) enhanced oxidation of benzophenone-8 by ferrate(VI): Mechanism and transformation products

Benzophenones (BPs) are commonly used as UV filters in cosmetics and plastics products and are potentially toxic to the environment. This paper presents kinetics and products of BPs oxidation by ferrate(VI) (FeO42−, Fe(VI)) promoted by permanganate (Mn(VII)) . Degradation of 10.0 µM 2,2′-dihydroxy-4-methoxybenzophenone (BP-8)were determined under different experimental conditions ([Mn(VII)] = 0.5–1.5 µM, [Fe(VI)] = 50–150 µM, and pH = 7.0–10.0). The addition of Mn(VII) traces to Fe(VI)-BP-8 solution enhanced kinetics and efficiency of the removal. Similar enhanced removals were also seen for other BPs (BP-1, BP-3, and BP-4) under optimized conditions. The second-order rate constants (k, M−1s−1) of the degradation of BPs showed positive relationship with the energy of the highest occupied orbital (EHOMO). The possible interaction between Mn(VII) and BP-8 and the enhanced generation of Fe(V)/Fe(IV) and •OH was proposed to facilitate the oxidation of the target benzophenone, supported by in-situ electrochemical measurements, theoretical calculations and reactive species quenching experiments. Thirteen oxidation products of BP-8 suggested hydroxylation, bond breaking, polymerization and carboxylation steps in the oxidation. Toxicity assessments by ECOSAR program showed that the oxidized intermediate products posed a tapering ecological risk during the degradation process. Overall, the addition of Mn(VII) could improve the oxidation efficiency of Fe(VI).

Cosmetic Ingredient: Metabolism and Mechanism

As additives, scents, preservatives, stabilizers, surfactants, stains, and shine, a variety of chemical substances have been added into the creation of cosmetic, beauty, and personal care products. Many of these compounds, on the other hand, are bioactive, ecologically persistent, and have the potential to bioaccumulate, posing a major hazard to the environment and human health. To genuinely address this issue, new techniques and approaches are necessary. This review summarizes the use of preservatives, pigments, and UV filters in cosmetics. The mechanisms of toxicities of preservative, such as parabens, benzalkonium chloride, and chlorphenesin are illustrated. Parabens have non-cutaneous adverse health effects, including infertility, spermatogenesis, adipogenesis, and perinatal exposure effects. Benzalkonium chloride in preservative decreased cell viability and caused apoptotic cell death in vitro. Pigment also played an important role in cosmetics and, some pigmentations in cosmetics are made by heavy metal or have heavy metal as ingredients. Cadmium and Chromium are two commonly used heavy metal in cosmetics. UV filters absorb UV energy and transform it chemically, which can lead to breakdown and the formation of photo-unstable reactive intermediates. Future research may focus on the safety assessment of specific substance in the application of cosmetics.

Rapid Screening of 19 UV Filters in Cosmetics Using Swab Touch Spray Ionization Coupled with Quadrupole/Orbitrap High-Resolution Mass Spectrometry

Rapid Screening of 19 UV Filters in Cosmetics Using Swab Touch Spray Ionization Coupled with Quadrupole/Orbitrap High-Resolution Mass Spectrometry

Preparation and Characterization of Organic/Inorganic Composite UV Filter Microcapsules by Sol‐Gel Method

Octyl methoxycinnamate and butyl methoxydibenzoylmethane are organic UV filters with poor photostability and will become photoallergy or phototoxic substance when exposed to ultraviolet radiation. The organic UV filters coated by microcapsules can reduce the photodegradation and avoid direct contact with the skin. Through microencapsulation, the application of UV filters in cosmetics becomes more effective and safer. This study first used the sol‐gel method to create organic/inorganic composite UV filter microcapsules. We used sodium alginate as a shell material of the microcapsule to encapsulate UV filters. CaCO3 and tetraethyl orthosilicate (TEOS) were used as cross‐linking agents, and sorbitan monooleate (Span 80) and polyoxyethylenesorbitan monooleate (Tween 80) were used as emulsifiers in the interfacial polymerization method for preparation. The results indicated that the microcapsules with 3 g of CaCO3 cross‐linking agents had a similar particle size and better entrapment efficiency. The average sizes were 61.0 ± 4.9 μm and 48.6 ± 4.7 μm, and entrapment efficiencies were 75.3 ± 1.9% and 74.8 ± 1.7% for octyl methoxycinnamate and butyl methoxydibenzoylmethane, respectively. Utilizing sodium alginate as a cross‐linking agent is better than TEOS due to the higher calcium content. In vitro transdermal delivery analysis showed that the release rate became steady.

Determination of six ultraviolet filters in cosmetics by high performance liquid chromatography coupled with solid-phase extraction based on graphene sponge

A method for the simultaneous determination of six UV filters in cosmetics by high performance liquid chromatography (HPLC) coupled with solid-phase extraction (SPE) based on graphene sponge (GS) was established. The samples were extracted with methanol by ultrasonic, then cleaned up by home-made SPE cartridges and eluted with acetone. The six UV filters were separated on an Agilent Zorbax SB-C18 column (150 mm×4.6 mm, 5 μm). Methanol-water (95:5, v/v) was used as mobile phase and the detection wavelength was 340 nm. The results showed that the limits of detection (LODs, S/N=3) and the limits of quantification (LOQs, S/N=10) of the six UV filters were 0.08-1.82 μg/L and 0.26-6.07 μg/L, respectively. The correlation coefficients (r) were greater than 0.999 except 2-(2'-hydroxy-5'-methyl-phenyl) benzotriazole (r>0.997). The recoveries of the six UV filters were 61.1%-119.0%, and the relative standard deviations (RSDs) were less than 1% (n=6) at the three spiked levels of 20, 50 and 100 μg/L. The method is simple, rapid, sensitive and repeatable, and is suitable for the determination of the UV filters in cosmetics.

Pulmonary responses in rat lungs after intratracheal instillation of 4 crystal forms of titanium dioxide nanoparticles.

Titanium dioxide nanoparticles are widely used as UV filters in cosmetics and as a photocatalyst. We evaluated pulmonary responses to different crystal forms of TiO2 nanoparticles. We used 4 different TiO2 samples with similar specific surface areas (anatase, rutile, amorphous, and P25). Each sample was suspended in distilled water and intratracheally instilled to male Wister rats at the dose of 1 mg per rat. Five rats per group were sacrificed at 3 days, 1 month, and 6 months after instillation, and bronchoalveolar lavage fluid was collected from the right lung to determine the total cell count and polymorphonuclear cell (PMN) counts. The left lung tissues were stained with hematoxylin and eosin for the evaluation of inflammation and with elastica van Gieson for the evaluation of collagen deposition. The total cell counts and PMN counts of the amorphous and P25 of four samples showed a significant increase compared with the control group at 3 days after instillation. The inflammation rate of P25 also showed a significant increase compared with controls at 3 days. The collagen deposition rate in the alveolar duct of P25 increased significantly compared with controls from 3 days to 6 months. The other samples showed a mild response after instillation. Although the TiO2 nanoparticles used in this study had similar specific surface areas, there were different inflammatory responses in the rat lungs. Other factors, such as different production processes or the surface activities of particles, may have been responsible for the different responses.

Determination of fifteen water and fat-soluble UV filters in cosmetics by pressurized liquid extraction followed by liquid chromatography tandem mass spectrometry

An analytical method based on pressurized liquid extraction followed by high performance liquid chromatography tandem mass spectrometry was developed for the simultaneous analysis of fifteen organic UV filters.

Determination of 17 ultraviolet-filters in cosmetics by high performance liquid chromatography

An optimum HPLC method was developed for the simultaneous determination of 17 ultraviolet (UV)-filters in cosmetics, in which two UV-filters were included more than the 15 UV-filters specified in the Hygenic Standard for Cosmetics (HSC). Our research focused on the optimization of sample processing, chromatographic column, and mobile phase, in order to avoid the use of highly corrosive solvents as tetrahydrofuran (THF) and perchloric acid, which are used in the HSC method. The cosmetic sample was extracted by the mixed solution of THF/methanol/water. The target chemicals were separated on a Phenomenex PFP column (250 mm x 4.6 mm, 5 microm) in gradient elution mode using water solution (containing 0.1% formic acid) and 20% methanol solution of isopropyl alcohol (containing 0.1% formic acid) as mobile phases. The detection wavelengths were set at 311 nm and 280 nm. The results of recovery tests and samples analysis indicated that the developed method can be used to simultaneously determine the 17 UV-filters in cosmetics, accurately and reliably. It is a more universal analytical method than the HSC method because common HPLC pump without improvement to adapt to corrosive THF, can be used. At the same time, the quantitative accuracy can be improved because baseline separation of all target chemicals was achieved

Sunscreens: are they beneficial for health? An overview of endocrine disrupting properties of UV‐filters

Today, topical application of sunscreens, containing ultraviolet-filters (UV-filters), is preferred protection against adverse effects of ultraviolet radiation. Evidently, use of sunscreens is effective in prevention of sunburns in various models. However, evidence for their protective effects against melanoma skin cancer is less conclusive. Three important observations prompted us to review the animal data and human studies on possible side effects of selected chemical UV-filters in cosmetics. (1) the utilization of sunscreens with UV-filters is increasing worldwide; (2) the incidence of the malignant disorder for which sunscreens should protect, malignant melanoma, is rapidly increasing and (3) an increasing number of experimental studies indicating that several UV-filters might have endocrine disruptive effects. The selected UV-filters we review in this article are benzophenone-3 (BP-3), 3-benzylidene camphor (3-BC), 3-(4-methyl-benzylidene) camphor (4-MBC), 2-ethylhexyl 4-methoxy cinnamate (OMC), Homosalate (HMS), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA) and 4-aminobenzoic acid (PABA). The potential adverse effects induced by UV-filters in experimental animals include reproductive/developmental toxicity and disturbance of hypothalamic-pituitary-thyroid axis (HPT). Few human studies have investigated potential side effects of UV-filters, although human exposure is high as UV-filters in sunscreens are rapidly absorbed from the skin. One of the UV-filters, BP-3, has been found in 96% of urine samples in the US and several UV-filters in 85% of Swiss breast milk samples. It seems pertinent to evaluate whether exposure to UV-filters contribute to possible adverse effects on the developing organs of foetuses and children.

Exposure patterns of UV filters, fragrances, parabens, phthalates, organochlor pesticides, PBDEs, and PCBs in human milk: Correlation of UV filters with use of cosmetics

In order to assess potential risks of exposure to environmental chemicals, more information on concomitant exposure to different chemicals is needed. We present data on chemicals in human milk of a cohort study (2004, 2005, 2006) of 54 mother/child pairs, where for the first time, cosmetic UV filters, synthetic musks, parabens and phthalate metabolites were analyzed in the same sample along with persistent organochlor pollutants (POPs), i.e., organochlor pesticides and metabolites, polybrominated diphenylethers and polychlorinated biphenyls (PCBs). The two groups of chemicals exhibited different exposure patterns. Six out of seven PCB congeners and a majority of pesticides were present in all milk samples, with significant correlations between certain PCB congener and pesticide levels, whereas the cosmetic-derived compounds, UV filters, parabens and synthetic musks, exhibited a more variable exposure pattern with inter-individual differences. UV filters were present in 85.2% of milk samples, in the range of PCB levels. Comparison with a questionnaire revealed a significant correlation between use of products containing UV filters and their presence in milk for two frequently used and detected UV filters, 4-methylbenzylidene camphor and octocrylene, and for the whole group of UV filters. Concentrations of PCBs and organochlor pesticides were within ranges seen in Western and Southern European countries. For several POPs, mean and/or maximum daily intake calculated from individual concentrations was above recent US EPA reference dose values. Our data emphasize the need for analyses of complex mixtures to obtain more information on inter-individual and temporal variability of human exposure to different types of chemicals.

Identification and determination butylmethoxydibenzoylmethane in the presence benzophenone‐3 and ethylhexylmethoxycinnamate in suncare preparation

The protection of sun radiation is a problem on global level for all living organisms on Earth. The need of people for the overexposure to the UV radiation led human population towards finding novel ways of protection of this kind of radiation, in form of cosmetic preparations applied on the skin. So far, the high values of protection factors of preparations and total block preparations with sun protection factor of 50+ were achieved. Physical and chemical filters which absorb radiation are constituents of these preparations. European Union has set regulations as which substances and in what amounts could be used as UV absorbers. American FDA (Food and Drug Administration) also gave its list of the most frequently used UV absorbers in the sunscreen products, as well as their declared concentrations. The most frequently used concentrations of UV filters in cosmetics is between 0.1% and 10%. Concentrations of UV filters in sunscreen products have to be monitored in order to ensure that they are not less from the declared levels, on which depends the efficacy and safety of the product. Butyl methoxydibenzoylmethane (BMDM) is used as a UV-A filter in suncare products. Optimized high performance liquid chromatography method for BMDM determination in the presence of other UV filters in suncare preparations is presented in this paper. Determination was performed on C(8) reversed phase using UV detection at 357 nm and isocratic mobile phase of acetonitrile and 0.5% phosphoric acid (70 : 30 v/v). Proposed method has limit of detection of 0.058 microg mL(-1), limit of quantification 0.193 microg mL(-1) and linearity correlation coefficient of 0.9989. Commercially available products were analysed using the proposed method. All analysed samples complied with EU directives limit of BMDM content to no more than 5%.

Endocrine Active UV Filters: Developmental Toxicity and Exposure Through Breast Milk

Several UV filters exhibit endocrine activity. Evidence for transdermal passage and presence in the food chain (fish) suggests potential exposure of humans during development. Developmental toxicity was studied in rats for the estrogenic UV filters 4-methylbenzylidene camphor (4-MBC, 0.7, 7, 24, 47 mg/kg/day) and 3-benzylidene camphor (3-BC, 0.07, 0.24, 0.7, 2.4, 7 mg/kg/day) administered in chow to the parent generation before mating, during pregnancy and lactation, and to the offspring until adulthood. Neonates exhibited enhanced prostate growth after 4-MBC and altered uterine gene expression after both filters. 4-MBC and 3-BC delayed male puberty and affected reproductive organ weights of adult offspring. Interactions with the thyroid were noted. Expression and estrogen sensitivity of target genes and nuclear receptor coregulators were altered at mRNA and protein levels in adult uterus, prostate and brain. Female sexual behavior was affected by 4-MBC and 3-BC, estrous cycles by 3-BC. Classical endpoints exhibited LOAELs/NOAELs of 7/0.7 mg/kg/day for 4-MBC and 0.24/0.07 mg/kg/day for 3-BC. Molecular endpoints were affected by the lowest doses. In order to obtain information on human exposure, we conducted a monitoring study on human milk with three series of mother–child pairs (2004, 2005, 2006), with focus on cosmetic UV filters in relation to other endocrine disrupters. Methods for UV filter analysis followed the principles of European standardized methods for pesticide residue analysis (EN 15289). In cohorts 2004 and 2005, 78.8% of women reported use of product(s) containing cosmetic UV filters in a questionnaire, and 76.5% of milk samples contained these filters. Use of UV filters and concentration in human milk were significantly correlated. The results agree with the idea of transdermal passage of UV filters. They also indicate that it may be possible to reduce human exposure during critical periods such as pregnancy and lactation by transiently abstaining from use.

Proposed protocol for determination of photostability Part I: cosmetic UV filters

Synopsis The protocol described here has been developed to measure the stability of UV-B filters; a modified version is recommended for UV-A filters. It should be considered as a tool to predict the effectiveness remaining after exposure to UV-A and UV-B light. It is a simple and reliable in vitro model simulating conditions of actual use. The results show that each filter requires an appropriate choice and fine tuning of reproducible analytical conditions. While absolute values are directly influenced by uncertainties in irradiance (dosimetry), comparative measurements with respect to a known standard are very reliable.

Effects of the putative xenoestrogens Benzophenone-2 (BP2) and Octyl-methoxycinnamate (OMC) on gene expression in the rat pituitary

Based on the rat uterotrophic assay, Benzophenone-2 (BP2) and Octyl-methoxycinnamate (OMC), two frequently used UV-filters in cosmetics, have been recently accused as estrogenic endocrine disrupters. An estrogenic action requires induction of the estrogen receptor (ER) signalling pathway comprising ERα and ß and their splice variants like the truncated estrogen receptor protein 1 (TERP1). Other known modulators of the ER signalling pathway are the aryl hydrocarbon receptor (AhR) and the estrogen receptor-related receptor 1 (ERR1). To further characterise the suggested estrogenic activity of OMC and BP2, the expression pattern of these nuclear receptors were measured in the pituitary of ovariectomized (ovx) rats. As reference compounds Estradiol-valerate (E2, ER ligand), Diethylstilbestrol (DES, ERR1 ligand) and 3-Methylcholanthrene (3MC, AhR ligand) were used. Adult ovx rats were treated orally once per day for 5 days with either E2, DES (0.6mg/kg each), 3MC (40mg/kg), or BP2 or OMC (10, 33, 100, 333mg/kg dissolved in olive oil). The control group received olive oil only. Gene expression was determined with real-time RT-PCR. A strong uterotrophic effect, cornification of the vaginal epithelium and a significant reduction of LHß-expression was observed in E2, DES and BP2 but not in OMC and 3-MC treated rats. Pituitary mRNA levels of ERα and ERR1 remained unaffected in all treatment groups, while levels of ERß and AhR were reduced to about 50% of the control group by E2 and DES (p<0.01). A profound increase in TERP1 expression occurred in the E2, DES and BP2 groups (about 200 fold, p<0.01).

Endocrine activity and developmental toxicity of cosmetic UV filters--an update.

UV filters represent a new class of endocrine active chemicals. In vitro, 8/9 chemicals showed estrogenic (MCF-7 cells), and 2/9 antiandrogenic activity (MDA-kb2 cells). Six/nine filters (benzophenone (Bp)-1, Bp-2, Bp-3, 3-benzylidene camphor (3-BC), 4-methylbenzylidene camphor (4-MBC), octyl-methoxycinnamate (OMC)) increased uterine weight in immature rats. 3-Benzylidene camphor and 4-MBC displaced 16alpha125I-estradiol from human estrogen receptor (ER)beta, not ERalpha. Developmental toxicity of 4-MBC (0.7-47 mg/kg body weight/day) and 3-BC (0.24-7 mg/kg), administered in chow was investigated in Long Evans (LE) rats. Weight gain of pregnant rats was reduced only by 3-BC, early postnatal survival rate and thymus weight by both compounds at higher doses. 4-Methylbenzylidene camphor and 3-BC delayed male puberty, and dose-dependently affected reproductive organ weights of adult male and female F1 offspring, with partly different effect patterns. Thyroid weight was increased by higher 4-MBC doses. Tissue-specific changes in mRNA levels of estrogen-regulated genes in prostate, uterus and brain regions, determined by real-time PCR, and in their response to acute estradiol challenge in adult gonadectomized offspring were observed. Lowest effective doses were 0.24 mg/kg/day for 3-BC and 7 mg/kg/day for 4-MBC. Fat tissue levels at 7 mg/kg 4-MBC (GC-MS) approached the range of UV filters in fish (Nagtegaal et al., 1997; Balmer et al., 2004).