Organic UV Filters Research Articles

Occurrence, spatial-temporal distribution and ecological risks of pharmaceuticals and personal care products response to water diversion across the rivers in Nanjing, China

Water diversion projects have been continuously used to alleviate water quality issues that arise during urbanization. However, studies about whether it has possible effects on the status of pharmaceutical and personal care products (PPCPs) are limited. In this study, the occurrence trends and spatial-temporal distribution characteristics of 50 PPCPs were investigated in surface water, suspended particulate matter (SPM) and sediments in Nanjing urban rivers under the background of the water diversion project from the Yangtze River to the Qinhuai River. In the four field campaigns that were embarked on April to July 2018, a total of 40, 38 and 24 PPCPs were detected in surface water, SPM and sediments, respectively, with overall concentrations of 138–1990 ng/L, 3214–33,701 ng/g and 12.1–109 ng/g dry weight (dw) among nine sampling sites. The excessive concentration of caffeine (20.6–905 ng/L) may be evidence of the direct discharge of untreated sewage and an obvious indicator of the overall concentrations of PPCPs. The PPCPs contamination levels in surface water were increased along with the direction of the water diversion in urban runoff, and decreased by 8–31% due to the increase in volume attributable to the water diversion. The distribution coefficients (Kd) of pollutants in the SPM-water phases (3.0–5.6 L/kg) were two orders of magnitude higher than those in the sediment-water phases (0.3–3.3 L/kg). And the positive correlations between their log Kow and SPM-water log Kd values indicated SPM was the important carrier determining the fate of organic UV filters. Furthermore, the results of ecological risk assessment demonstrated that although the increase in the volume of water caused by the water diversion reduced the overall ecological risks of PPCPs in urban rivers, the current contamination level still represents high risks to algae and fish.

Systemic availability of lipophilic organic UV filters through dermal sunscreen exposure

BackgroundChemical UV filters are common components in sunscreens and cosmetic products and used to protect the skin against harmful effects of sunlight like sunburn. However, the effectiveness of sunscreens in the prevention of skin cancer is in some parts still controversial. Meanwhile, questions about negative effects of the chemical UV filters on human health arise and request an effective risk assessment. Real-life exposure data in humans after application of these products are still rare. Thus, we explored whether and to what extent UV filters are absorbed through the skin into the human body. Material and methodsPlasma and urine samples from 20 healthy volunteers were collected before, during and after a real-life exposure scenario (1st application: 2 mg/cm2; 2nd and 3rd (after 2 and 4 h): 1 mg/cm2 each) using a commercial sunscreen formulation for one day. These samples were analyzed for their content of the currently prominent UV filters octocrylene and avobenzone as well as 2-cyano-3,3-diphenylacrylic acid (CDAA) as the main octocrylene metabolite by using different liquid chromatography electrospray-ionization tandem mass spectrometric procedures. ResultsFollowing dermal sunscreen exposure, avobenzone, octocrylene and CDAA reached concentrations up to 11 μg/L, 25 μg/L and 1352 μg/L in plasma. In urine detection rates of avobenzone and octocrylene were low while CDAA showed a high detection rate and reached up to 5207 μg/g creatinine. Kinetic models could be fitted for octocrylene and CDAA in plasma and CDAA in urine. Concentration peaks were reached between 10 and 16 h after first application and half-life periods were in the range of 1.5 to 2 days. The lipophilic UV filter octocrylene and its metabolite CDAA showed a much slower elimination than other more hydrophilic UV filters. Concordantly, the metabolite CDAA in particular showed a markedly increased renal excretion over the whole sampling period and indicated high internal exposure to OC. DiscussionReal-life sunscreen usage leads to considerable bioavailability of organic UV filters and their metabolites which is rarely seen for other environmental exposures. A combined monitoring of the parent compound and its metabolites is important to fully address internal exposure to the UV filter in humans. Considering the kinetic profiles a prolonged systemic release due to depot formation in skin and a potential accumulation through multi-day exposure is presumed. High in-vivo loads call for a critical toxicological assessment of the UV filters and their metabolites.

Using ordered mesoporous silica SBA-15 to limit cutaneous penetration and transdermal permeation of organic UV filters.

Avobenzone (AVO), oxybenzone (OXY), and octyl methoxycinnamate (OMC), are widely used UV filters. The aim of this study was to investigate the effect of incorporation in mesoporous silica (SBA-15) on their cutaneous deposition and permeation. Stick formulations containing "free" and "incorporated" UV filters (SF1 and SF2, respectively) were prepared and characterized with respect to their physicochemical, thermal, and functional properties. Cutaneous delivery experiments using porcine skin with quantification by UHPLC-MS/MS, demonstrated that skin deposition of AVO and OXY after application of SF2 for 6 and 12 h was significantly lower than that from SF1 at each time-point (Student t-test, p < 0.05): e.g. OXY permeation across the skin was 30-, 12- and 1.5-fold lower after 6, 12 and 24 h, respectively, following application of SF2. Cutaneous biodistribution profiles of AVO and OXY to 800 µm evidenced a significant decrease in the amounts in the viable epidermis and dermis. In contrast, deposition of the more lipophilic OMC was not significantly different (p ˃ 0.05). In vitro photoprotective efficacy results demonstrated that adsorption/entrapment of UV filters enhanced the sun protection factor by 94%. In conclusion, SBA-15, an innovative mesoporous material, increased photoprotection by UV filters while reducing their cutaneous penetration and transdermal permeation.

Sorption and desorption of organic UV filters onto microplastics in single and multi-solute systems

Sorption studies of organic pollutants by microplastics (MPs) in single-solute systems are well established in the literature. However, actual aquatic environments always contain a mixture of contaminants. Prediction of the fate and biological effects of MPs-mediated chemical exposure requires a better understanding of sorption-desorption processes of multiple organic contaminants by MPs. In this study, the altered sorption and desorption behaviors of individual organic UV filters (BP-3 and 4-MBC) in the presence of cosolutes (BP-3, 4-MBC, EHMC and OC) on two types of MPs (LDPE and PS) were examined. In most cases, co-occurrence of other organic UV filters appeared to have an antagonistic effect on the sorption of primary solute, which was consistent with trends found in previous studies. Nevertheless, the sorption uptake of 4-MBC as primary solute on PS was enhanced in the presence of cosolute(s), arising presumably from solute multilayer formation caused by laterally attractive π-π interactions between adsorbed cosolute(s) and 4-MBC molecules. Such formation of multilayer sorption in multi-solute systems depends on the solute hydrophobicity and concentration as well as inherent sorptivity of MPs. Our further desorption experiments revealed that the bioaccessibility of primary solute was significantly elevated with cosolutes, even though competitive sorption was observed under the same experimental conditions. These findings supplement the current knowledge on sorption mechanisms and interactions of multiple organic contaminants on MPs, which are critical for a comprehensive environmental risk assessment of both MPs and hazardous anthropogenic contaminants in natural environments.

Investigation of textural properties and photocatalytic activity of PbO/TiO2 and Sb2O3/TiO2 towards the photocatalytic degradation Benzophenone-3 UV filter

Benzophenone-3 (BP-3) is a widely used organic UV filter in sunscreen which has been detected in surface and groundwater. BP-3 can affect the aquatic environment and human health. In this study, PbO/TiO2 and Sb2O3/TiO2 photocatalyst were synthesized for the photocatalytic degradation of Benzophenone-3 (BP-3) and various degradation parameters such as initial pH value, initial concentration, and the dose of catalysts were optimized. Two different TiO2 based catalysts PbO/TiO2 and Sb2O3/TiO2 were synthesized by hydrothermal method. Synthesized photocatalysts were characterized by X-ray diffraction pattern (XRD), scanning electron microscope (SEM), Energy Dispersive Spectroscopy (EDS), BET and UV–Vis DRS techniques. Molar ratio variation of PbO and Sb2O3 with respect to TiO2 significantly affected the surface area, structure, and bandgap of photocatalyst and hence the variation in degradation efficiency of the photocatalyst was observed. The BP-3 can be completely degraded by using PbO/TiO2 within 120 min under UV-C irradiation. The highest degradation of BP-3 was obtained for the 20 µM concentration at pH 7 when the dose was adjusted to be 0.75 g/L. However, negligible degradation of BP-3 was demonstrated in the absence of a catalyst. Moreover, with the catalysts PbO/TiO2 and Sb2O3/TiO2, BP-3 followed the pseudo-first-order kinetics with a rate constant of 3.58 × 10−2 min−1 and 0.92 × 10−2 min−1 respectively. Electron paramagnetic resonance (EPR) spectrum with three distinct peaks with an intensity of 1:1:1 showed the presence of TEMP-1O2 adduct which suggested the generation of 1O2 (singlet oxygen) in both catalysts. The plausible mechanism of BP-3 degradation was proposed by the Gas chromatography-mass spectrometry (GC-MS) analysis which showed the formation of pentamethyl- and 5-Hydroxy-7-methoxy-2-methyl-3-phenyl-4-chromenone byproducts on BP-3 photocatalytic degradation by the synthesized catalyst.

Occurrence and Environmental Distribution of 5 UV Filters During the Summer Season in Different Water Bodies

Organic UV filters are used worldwide in various personal care products as well as textiles, paints, plastic, food, and adhesives. They are main ingredients in sunscreen lotions that are used heavily by beachgoers in the summer season. There is thus an increasing concern regarding the fate of organic UV filters in the environment and their impact on living organisms. Many of the UV filters in use are hydrophobic and are expected to accumulate in the sediment phase in aquatic systems, but this has yet to be validated in situ. We targeted the UV filters benzophenone 3 (BP3), butyl methoxydibenzoylmethane (BMDBM), diethylhexyl butamido triazone (DBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), and methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT) in a freshwater lake and in a coastal bay in order to understand their distribution during summer 2016. Further, we examined their environmental partitioning by collecting samples from the surface water, the sediment phase, and water surface microlayer (SML). We show for the first time the presence of DBT, BEMT, and MBBT in environmental matrices (water, SML, and sediment). Notably, these UV filters were detected at low amounts in surface waters with maximum concentrations of 9.9 ng/L for DBT, 18.4 ng/L for BEMT, and below detection limits for MBBT and somewhat higher concentrations in the SML, with maximum concentrations of 43.3 ng/L for DBT, 5625.4 ng/L for BEMT, and 45.6 ng/L for MBBT. These filters were detected at even greater concentrations in the sediments, with maximum concentrations of 652.6 ng/g for DBT, 115.0 ng/g for BEMT, and 75.2 ng/g for MBBT (dry weight sediment). We also performed controlled laboratory experiments to determine their partitioning behavior, and we verified the actual solubility of many of the filters. This will help in determining the environmental fate and finally lead to a better risk assessment of these compounds. Together, these results corroborate the hypothesis that hydrophobic UV filters accumulate in the sediment phase and highlight the importance of discerning whether these UV filters impact the benthic community and their potential for bioaccumulation.

Quantification of prominent organic UV filters and their metabolites in human urine and plasma samples

Monitoring human exposure to chemical UV filters is essential for an accurate assessment of the health risk caused by the resorbed compounds. We developed different procedures for the determination of the prominent UV filters octocrylene (OC), avobenzone (AVO) and 2-ethylhexyl salicylate (EHS) as well as for two OC and EHS metabolites in human urine and OC, AVO and 2-cyano-3,3-diphenylacrylic acid (CDAA) in plasma samples using liquid chromatography-tandem mass spectrometry (LC–MS/MS).Since the development of a multi-method for all analytes proved to be difficult, three different procedures were established for the determination of AVO, OC and its metabolite CDAA in urine and plasma as well as for EHS and its metabolite 5-hydroxy-EHS in urine. The methods have been validated with good sensitivity, precision and accuracy. The procedures were satisfactorily applied to the determination of the target compounds in human samples collected from volunteers after sunscreen application. These new analytical procedures can provide information on the internal exposure to the UV filters OC, AVO and EHS, which has been little studied.

Discovery of Novel UV-Filters with Favorable Safety Profiles in the 5-Arylideneimidazolidine-2,4-dione Derivatives Group.

Effective protection from the harmful effects of UV radiation may be achieved by using sunscreens containing organic or inorganic UV filters. The number of currently available UV filters is limited and some of the allowed molecules possess limitations such as systemic absorption, endocrine disruption properties, contact and photocontact allergy induction, and low photostability. In the search for new organic UV filters we designed and synthesized a series consisting of 5-benzylidene and 5-(3-phenylprop-2-en-1-ylidene)imidazolidine-2,4-dione (hydantoin) derivatives. The photoprotective activity of the tested compounds was confirmed in methanol solutions and macrogol formulations. The most promising compounds possessed similar UV protection parameter values as selected commercially available UV filters. The compound diethyl 2,2′-((Z)-4-((E)-3-(4-methoxyphenyl)allylidene)-2,5-dioxoimidazolidine-1,3-diyl)diacetate (4g) was characterized as an especially efficient UVA photoprotective agent with a UVA PF of 6.83 ± 0.05 and favorable photostability. Diethyl 2,2′-((Z)-4-(4-methoxybenzylidene)-2,5-dioxo- imidazolidine-1,3-diyl)diacetate (3b) was the most promising UVB-filter, with a SPFin vitro of 3.07 ± 0.04 and very good solubility and photostability. The main photodegradation products were geometric isomers of the parent compounds. These compounds were also shown to be non-cytotoxic at concentrations up to 50 µM when tested on three types of human skin cells and possess no estrogenic activity, according to the results of a MCF-7 breast cancer model.

Preparation and SPF Evaluation of Sunscreen Cream Containing Titanium Dioxide

Titanium dioxide, a physical sunscreen, is a metal oxide which reflects and disperses incident UV radiation by an optical mechanism. Sun protect factor (SPF) indicates the level of protection from UV rays. This study aims to prepare titanium dioxide sunscreen cream and evaluate its SPF. Sunscreen cream was first prepared by emulsification method, and then mixed with titanium dioxide. As a result, the sunscreen cream loaded with 5% titanium dioxide had good visual performance, physical stability, and medium UV protection effect with SPF 20+.&#x0D; Keywords&#x0D; Titanium dioxide, sunscreen, SPF.&#x0D; References&#x0D; [1] K. Morabito, N.C. Shapley, et al. Review of sunscreen and the emergence of non‐conventional absorbers and their applications in ultraviolet protection, International journal of cosmetic science. 33(5) (2011), 385-390. https://doi.org/10.1111/j.1468-2494.2011.00654.x.[2] Schalka Sergio, Reis Vitor Manoel Silva dos. Sun protection factor: meaning and controversies, Anais brasileiros de dermatologia. 86(3) (2011) 507-515. [3] Serpone Nick, Dondi Daniele, et al. Inorganic and organic UV filters: Their role and efficacy in sunscreens and suncare products, Inorganica Chimica Acta. 360(3) (2007) 794-802. https://doi.org/10.1016/j.ica.2005.12.057.[4] COLIPA. Method for in vitro determination of uva protection, (2011), 17-19.[5] Couteau Céline, Faure Aurélie, et al. Study of the photostability of 18 sunscreens in creams by measuring the SPF in vitro, Journal of pharmaceutical and biomedical analysis. 44(1) (2007) 270-273. https://doi.org/10.1016/j.jpba.2007.01.052.[6] ISO (2010), Biological evaluation of medical devices-Part 10: Tests for irritation and skin sensitization, 10.[7] OECD (2015), OECD Guideline for testing of chemicals: Acute Dermal Irritation/Corrosion, 404.&#x0D; &#x0D; &#x0D;

Elimination efficiency of organic UV filters during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent

The efficiency of elimination of organic UV filters by ozonation and UV254nm/H2O2 processes was assessed and predicted in simulated treatments of sewage-impaired drinking water and wastewater effluent in bench-scale experiments. Second-order rate constants (k) for the reactions of the eight UV filters with ozone and OH were determined by quantum chemical calculations and competition kinetics methods, respectively. The UV filters containing phenolic (ethylhexyl-salicylate, homosalate, and benzophenone-3) and olefinic moieties (4-methylbenzylidene-camphor, benzyl-cinnamate, and 2-ethylhexyl-4-methoxycinnamate) showed high ozone reactivity (k ≥ 8 × 104 M−1s−1 at pH 7), while those without such electron-rich moieties (isoamyl-benzoate and benzophenone) were ozone-refractory. All the UV filters showed high OH reactivity (k ≥ 6.2 × 109 M−1s−1). In concordance with the rate constant information, the phenolic and olefinic UV filters were efficiently eliminated by ozone treatment, requiring specific ozone doses of <0.5 mgO3/mgDOC for ∼100% elimination. The UV filters were eliminated by ≤ 38% at a UV fluence of 1500 mJ/cm2 in the UV254nm-only treatment. Rapid photoisomerisation between the E and Z geometric isomers was observed for the olefinic UV filter, benzyl-cinnamate. The addition of H2O2 (10 mg/L) greatly enhanced the elimination of all UV filters, indicating that OH was the main contributor to their elimination in the UV254nm/H2O2 treatment. A chemical kinetics approach developed previously for ozonation and UV/H2O2 processes was shown to predict the elimination of the UV filters in the tested water matrices reasonably well, demonstrating that the chemical kinetics method can be used for a priori prediction of micropollutant elimination in oxidative treatment processes for potable reuse of municipal wastewater effluents.

Assessment of the cytotoxicity and genotoxicity of homosalate in MCF-7.

UV filters should be determined a strict toxicological safety prior to approval. Homosalate (HMS) is one of the most widely used organic UV filter. HMS accumulates in aquatic biota ecosystems and humans through the food chain; therefore, it is important to consider the effects on health and know its mechanisms of action. The study aimed to evaluate the cytotoxic and genotoxic effects of HMS in MCF-7 cell line. Cell viability was examined by the 3-(4,5-dimethylthiazol-2-yl)2,5-diphenyl tetrazolium bromide (MTT) and cell membrane integrity by the lactate dehydrogenase release assays (LDH), and genotoxicity by using the micronucleus test at 250, 500, 750, 1000, 1500, and 2000µM concentrations with the human breast cell line MCF-7. Homosalate affected the cell viability dose-dependently at a concentrations of above 1000µM. Micronucleus formation was significantly induced at 750 and 1000µM within 24hours due to an increase in cytostatic effect, the cell viability of HMS decreased to 57% at a concentration of 2000µM, and a sufficient number of binucleated cells could not be obtained to count. Homosalate was also clastogenic when the cells were incubated at cytotoxic concentrations. These results suggest that homosalate can be considered as a cytotoxic and genotoxic substance.

Development of transient mutagenic activity following the chlorination of the sunscreen UV filter dioxybenzone (benzophenone-8) in bromide-rich water.

The mutagenicity of four organic UV filters namely oxybenzone (benzophenone-3), dioxybenzone (benzophenone-8), avobenzone, and octyl methoxycinnamate, in chlorinated bromide-rich water (artificial seawater) was investigated. Mutagenicity was evaluated using Ames test in Salmonella typhimurium TA98 without S9 mix. Chemical analysis using high-resolution mass spectrometry was carried out to elucidate the mutagenic transformation products. Among the studied UV filters, only dioxybenzone exhibited a clear mutagenic activity following chlorination in seawater at ratio 1:10 (UV filter:chlorine). In contrast, no mutagenic activity was detected when chlorine was added at higher doses (ratio 1:1000). High-resolution mass spectrometry analysis showed that mutagenic extracts contained several brominated transformation products of dioxybenzone. Time course analysis of the transformation products at increasing chlorine doses showed that they were unstable and disappeared more quickly at higher chlorine doses. This instability explained the absence of mutagenic activity of dioxybenzone when 1000-fold excess chlorine was added, as no transformation products were detected. Relevance of these findings to the context of swimming pool is discussed. Further investigations taking into consideration the mutagenicity of not only the intermediate transformation products but also the final disinfection byproducts are needed to determine the overall impact of high levels of chlorine on the overall mutagenicity. This study highlights the importance of considering the reactivity of organic UV filters and their transformation products in disinfected recreational waters when sunscreen formulations are prepared.

Use of Vegetable Oils to Improve the Sun Protection Factor of Sunscreen Formulations

Some vegetable oils have many biological properties, including UV-absorbing capacity. Therefore, their use has been suggested to reduce the content of organic UV-filters in sunscreen products. In this work, we investigated the feasibility of developing oil-based vehicles with a high sun protection factor (SPF) using pomegranate oil (PMG) and shea oil (BPO) in association with different percentages of organic UV-filters (octyl– methoxycinnamate, butyl methoxydibenzoylmethane, and bemotrizinol). We characterized the spreadability, occlusion factor, pH, and required hydrophilic lipophilic balance of the resulting formulations, and did not observe relevant differences due to the incorporation of vegetable oils. The in vitro spectrophotometric determinations of SPF values highlighted that the addition of BPO (1% (w/w)) and PMG (1% (w/w)) resulted in an increase in SPF in comparison with the same formulations that contained only organic UV-filters. The SPF increase was more significant for the formulations that contained lower amounts of organic UV-filters. The results of this study supported the hypothesis that including suitable vegetable oils in sunscreen formulations could be a promising strategy to design products with a lower content of organic UV-filters.

Photoprotection assessment of olive (Olea europaea L.) leaves extract standardized to oleuropein: In vitro and in silico approach for improved sunscreens

Olive leaves contain higher amount of polyphenols than olive oil and represent a waste product from olive harvest and pruning of olive trees. The most abundant compound in olive leaves is oleuropein. Benefits of the topical application of olive leaves extract were previously reported, but little information is available on its photoprotective potential and the result of the association of this extract with organic UV filters in topical sunscreen formulations. The olive leaves extract photoprotective potential is less explored for both oral and topical photoprotection in comparison with other plants extracts and polyphenols, such as Polypodium leucotomos extract and resveratrol. There are increasing efforts towards developing more efficient sunscreens and a photoprotection assessement along with a better understanding of the photochemistry of naturally occurring sunscreens could aid the design of new and improved commercial sunscreen formulations. This study was designed to investigate the photoprotective potential of olive leaves extract standardized for oleuropein performing a set of in vitro and in silico tools as an innovative approach, highlighting yeast assays, in vitro Sun Protection Factor (SPF) and molecular modelling studies of UV absorption. This study supports the use of olive leaves extract for photoprotection, as an effective photoprotective, anti-mutagenic and antioxidant active, also showing a synergistic effect in association with UV filters with an improvement on in vitro SPF of sunscreen formulations.

Two-generational effects of Benzophenone-3 on the aquatic midge Chironomus riparius

Organic UV-filters are emergent contaminants continuously released into the aquatic ecosystems. These compounds are persistent showing potential for bioaccumulation. Partial life-cycle tests may underestimate the toxicity of UV-filters especially since these compounds have shown to act as endocrine disruptors. In the present study, the benthic aquatic insect Chironomus riparius was exposed to a gradient of Benzophenone-3 (BP3) concentrations over two generations to assess effects over a full life cycle from the first-instar larvae in the parental (P) generation (emergence, fecundity and fertility) until emergence in the subsequent generation (filial – F1). Recovery from exposure was also assessed after one generational exposure. Our results showed that concentrations of up to 8mg BP3/kg, elicited no effects regarding emergence rate and development time of C. riparius in the P generation. Our results also showed that C. riparius fecundity was not affected by BP3 exposure, but a strong dose-response relationship was observed for fertility with none of the egg ropes hatching at 8mg BP3/kg. Regarding effects observed in the F1 generation, emergence and development time were impaired by continuous exposure to BP3. Moreover, reduced emergence and changes in development time were observed in the F1 generation maintained in control/clean conditions but whose parents were exposed to BP3. Results found in this two-generational study clearly show reproductive effects of BP3 on C. riparius that would not be detected using standard tests. Full life cycle and multigenerational assays are critical to properly evaluate the population level effects of endocrine disrupting compounds such as organic UV-filters.

Nanostructured Zn-Ti layered double hydroxides with reduced photocatalytic activity for sunscreen application

The harmful effects of long-term UV exposure on human skin are increasingly understood these days, and therefore, the use of topical sunscreen products containing UV filters has significantly increased. Although the currently used organic and inorganic UV filters are effective UV absorbers, they may cause several problems such as high photoreactivity, photodegradation, and generation of reactive oxygen species leading to serious skin damages including skin cancer. Therefore, the development of safer, skin-compatible, photostable, and more effective photoactive ingredients is critical. In this study, a Zn-Ti layered double hydroxide (Zn-Ti LDH) was prepared using a hydrothermal method, and its properties as a sunscreen additive were evaluated and compared to those of nano-TiO2 and nano-ZnO. Physical characterization confirmed the formation of a highly stable crystalline LDH structure. Scanning electron microscopy analysis revealed the formation of two-dimensional nano-flakes and layered structure. The optical properties of Zn-Ti LDH analyzed by diffuse reflectance UV-Vis showed higher UV reflection properties and lower absorption properties in comparison to TiO2 and ZnO. Zn-Ti LDH exhibited substantially lower levels of photocatalytic activity towards the degradation of methylene blue at both 365 nm and 254 nm which indicates increased safety of Zn-Ti LDHs for use as UV filters in topical sunscreen applications.

Calibration parameters for the passive sampling of organic UV filters by silicone; diffusion coefficients and silicone–water partition coefficients

In recent years, organic ultraviolet filters (UVFs) received considerable attention as a group of emerging contaminants, including in Australia where the use of UVFs is particularly relevant. Passive sampling using polymers has become widely used for routine monitoring of chemicals in the aquatic environment. Application of passive samplers for monitoring chemicals in the water relies on calibration data such as chemical's polymer-water partition coefficient (Kpw) and diffusion coefficients in the sampling material (Dp), for understanding uptake and kinetic limitations. In the present study, Kpw and Dp for nine UVFs were estimated. Kpw values were determined in different water – polymer partition experiments where (1) a given mass of chemicals was dosed into the water and (2) into the polymer. Diffusion coefficients were determined using the stacking method. The estimated log Kpw and log Dp ranged from 2.9 to 6.4 L kg−1 and -11.1 to −10.5 m2s-1, respectively. The sufficient high Dp allows application of kinetic models that only consider water boundary-controlled uptake for converting silicone sampler uptake into an aqueous phase concentration using the presented Kpw.

Per capita loads of organic UV filters in Australian wastewater influent

Per capita loads of six UV filters were estimated in wastewater influent samples from 36 wastewater treatment plants in Australia collected over a weekend period during the 2016 Australian Census. Of the analysed samples, 99% contained at least one of the target compounds. Phenyl benzimidazole sulfonic acid (PBSA) was the most prevalent (99%), followed by benzophenone 4 (BP4) (97%), benzophenone 3 (BP3) (87%), benzophenone 1 (BP1) (84%), 4-methylbenzylidene camphor (4-MBC) (22%) and isoamyl 4-methoxycinnamate (IMC) (1.5%). The highest concentrations were 3780 and 5070 ng L−1 for PBSA and BP4, respectively. Total per capita UV filter loads in influent across all plants were calculated using population data from the Australian Census and ranged from 0.21 to 3.4 mg day−1 person−1. Notably, a relationship was found between latitude and total per capita daily mass load of UV filters with an increase in mass load from southern to northern catchments. Compared to international studies, mass loads were generally similar with higher loads of BP4 found in Australia. This study provides insight into the occurrence of UV filters in influent wastewater from across Australia and provides the first comprehensive nationwide baseline of UV filter loads.

Rapid characterization of organic UV filters and their photoproducts in sunscreens by thermal desorption electrospray ionization mass spectrometry for the photostability study

UV filters and their photoproducts in sunscreen formulations are directly characterized by TD-ESI/MS. This is a highly viable strategy to study the photostability of highly complex and diverse sunscreen formulations in the market.

First application of carbon-based screen-printed electrodes for the voltammetric determination of the organic UV filters oxybenzone and octocrylene

A new voltammetric methodology is proposed for the simultaneous determination of the organic UV filters oxybenzone (benzophenone 3, BP3) and octocrylene (OC) in personal care products and in wastewater extracts. It is based on previous adsorptive stripping voltammetric (AdSV) methods developed for hanging mercury drop electrodes, adapted to the special characteristics of carbon-based screen-printed electrodes. Among the carbon substrates tested, regular carbon screen-printed devices exhibited the best performance, with detection limits of 4.8 and 6.6 μmol L−1 and linearity ranges of 16–400 and 22–400 μmol L−1 for BP3 and OC, respectively, and, as compared to mercury electrodes, with the advantages of environmental safety, easy of use, low cost and compatibility with automation and flow measurements. The methodology has been successfully tested in real samples and compared to the standard methodology by liquid chromatography – tandem mass spectrometry (LC-MS/MS).