Selected UV Filters Research Articles

Assessing the Fate of Benzophenone-Type UV Filters and Transformation Products during Soil Aquifer Treatment: The Biofilm Compartment as Bioaccumulator and Biodegrader in Porous Media.

The fate of selected UV filters (UVFs) was investigated in two soil aquifer treatment (SAT) systems, one supplemented with a reactive barrier containing clay and vegetable compost and the other as a traditional SAT reference system. We monitored benzophenone-3 (BP-3) and its transformation products (TPs), including benzophenone-1 (BP-1), 4,4'-dihydroxybenzophenone (4DHB), 4-hydroxybenzophenone (4HB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), along with benzophenone-4 (BP-4) and avobenzone (AVO) in all involved compartments (water, aquifer sediments, and biofilm). The reactive barrier, which enhances biochemical activity and biofilm development, improved the removal of all detected UVFs in water samples. Among monitored UVFs, only 4HB, BP-4, and AVO were detected in sediment and biofilm samples. But the overall retained amounts were several orders of magnitude larger than those dissolved. These amounts were quantitatively reproduced with a specifically developed simple analytical model that consists of a mobile compartment and an immobile compartment. Retention and degradation are restricted to the immobile water compartment, where biofilm absorption was simulated with well-known compound-specific Kow values. The fact that the model reproduced observations, including metabolites detected in the biofilm but not in the (mobile) water samples, supports its validity. The results imply that accumulation ensures significant biodegradation even if the degradation rates are very low and suggest that our experimental findings for UVFs and TPs can be extended to other hydrophobic compounds. Biofilms act as accumulators and biodegraders of hydrophobic compounds.

Voltammetric determination of organic UV filters by carbon paste electrodes modified with pyridinium-based ionic liquids

The rapid and sensitive voltammetric determination of organic UV filters benzophenone-3 (BP-3) and avobenzone (AVO) was performed by an ionic liquid carbon paste electrode (IL-CPE). Namely, the synthesized pyridinium-based ILs, 1-butyl-3-methylpyridinium chloride ([N–C4–3C1Py]Cl) and 1-ethoxyethyl-3-methylpyridinium chloride ([N–C2OC2–3C1Py]Cl) were compared as bulk CPE modifiers for BP-3 determination. [N–C4–3C1Py]Cl-CPE showed more favorable interactions with the target analyte, and it was tested for AVO determination, too. Cyclic voltammetric (CV) studies suggested that the irreversible electrode reaction is adsorption controlled in the case of both UV filters. Also, the square-wave adsorptive stripping voltammetric (SW-AdSV) method was optimized for quantifying selected UV filters. In the model solutions, the linear calibration curve was obtained by the SW-AdSV method in the concentration range from 0.05 to 0.89 μg mL−1 at pH 3.0 for BP-3 (Eacc = −0.7 V, tacc = 100 s), and from 0.05 to 1.77 μg mL−1 at pH 11.98 for AVO (Eacc = 0.2 V, tacc = 100 s). The evaluated limit of detection (LOD) was 0.015 μg mL−1 in both cases, while the relative standard deviation (RSD) was lower than 1.5%. The affordable IL-based voltammetric sensor fulfills the main requirements for application in real samples due to an adequate selectivity towards selected analytes in the presence of interferents usually found in swimming pool water. Therefore, the BP-3 and AVO were quantified in a swimming pool water matrix with good repeatability and recovery. The obtained results demonstrate an excellent potential of the IL-CPEs, especially of the [N–C4–3C1Py]Cl-CPE, for determining selected UV filters in various real samples.

Correlation between in vitro and in silico determined sun protection factor of selected UV filters

Correlation between in vitro and in silico determined sun protection factor of selected UV filters

Investigation of simultaneous multiple UV filters degradation efficiency of plasmonic Ag@AgCl photocatalyst in the aquatic environment under sunlight irradiation.

UV filters as an important class of emerging organic pollutants are continuously released into and transported between the aquatic environments. So, the removal of these compounds from aquatic environments is of great importance. This study was conducted to evaluate the simultaneous photodegradation of three widely used UV filter compounds (4-methylbenzylidene camphor, 2-ethylhexyl 4-(dimethylamino) benzoate, ethylhexyl methoxycinnamate), in an aqueous environment under sunlight and Ag@AgCl photocatalyst integrated with plasmonic effect. The plasmonic Ag@AgCl nanocomposite was constructed via photochemical conversion and photoreduction. The enhanced photocatalytic performance can be attributed to the surface plasmon resonance effect of the silver nanoparticles and the hybrid effect caused by AgCl. For the monitoring of the target compounds' degradation before and after photodegradation, an optimized method based on membrane-protected micro-solid-phase extraction coupled with gas chromatography-mass spectrometry (GC-MS) was employed. The simultaneous degradation of selected UV filters was also further investigated in contaminated real samples (river water) and the results showed that the matrix constituents could diminish the photocatalytic degradation efficiency.

Influence of physical–mechanical properties on SPF in sunscreen formulations on ex vivo and in vivo skin

The sun protection factor (SPF) is related to the selected UV filters. The objective of this study was to evaluate and compare the rheological behavior and texture profile of two sunscreen formulations and to correlate these data with the obtained SPF values. Two formulations (F1 and F2) were developed with the same type and amount of UV filters – whereby one of them also contained ethoxylated lanolin as additional film former (F2). Their rheological behavior, texture profile and in vitro and in vivo SPF were analyzed. The film-forming properties were evaluated by skin profilometry and diffuse reflectance spectroscopy. The structures of the formulations were examined by two-photon tomography combined with fluorescence lifetime imaging, and the penetration profile into the stratum corneum was investigated by tape stripping. The formulation with lanolin presented lower and constant values for physical–mechanical parameters, with a higher and better reproducible SPF. Both formulations did not penetrate the viable epidermis. In conclusion, formulations with better surface deposition on the skin surface can influence the film formation and, consequently, improve the SPF. These findings are important to improve the efficacy of sunscreen formulations and reduce the addition of UV filters.

The presence of selected UV filters in a freshwater recreational reservoir and fate in controlled experiments

UV filters present in sunscreen and other cosmetics are directly released into the environment during aquatic recreational activities. The extent to which the wide range of UV filters pose a risk to the environment remains unclear. This study investigated the occurrence and dissipation of selected organic UV filters at a recreational site (Enoggera Reservoir, Queensland, Australia) over 12 h. Furthermore, different possible degradation processes were investigated in a controlled off-site experiment with surface water exposed to natural light. Half-lives were estimated for ten UV filters. In Enoggera Reservoir, seven UV filters were detected, of which the most prevalent were octocrylene, avobenzone (BMDBM) and enzacamene (4-MBC). Summed concentrations of the seven UV filters ranged from 7330 ng L−1 at 13:00 h to 2550 ng L−1 at 21:00 h. In the degradation experiment, four UV filters showed no significant change over time. The fate of these compounds in the environment is likely to be mainly influenced by dispersion. Half-lives of the remaining UV filters were 6.6 h for amiloxate (IMC), 20 h for benzophenone 1, 23 h for octinoxate (EHMC), 30 h for 3-benzylidene camphor, 34 h for 4-MBC and 140 h for dioxybenzone (BP8). The degree of susceptibility to photodegradation and biodegradation was generally consistent within a structural class. The fate and half-lives of UV filters are variable and should be considered on a per site basis when assessing environmental risk.

Annual release of selected UV filters via effluent from wastewater treatment plants in Australia

Studies conducted globally have identified wastewater effluent as a key source of UV filters released into the aquatic environment. We assessed the annual release of UV filters from wastewater treatment plant effluent in Australia and evaluated the removal of these chemicals during wastewater treatment. Effluent samples were collected from 33 sites alongside matching influent samples. Sample collection predominately occurred during the Australian Census in August 2016, which allowed for accurate per capita normalisation of the results. A subset of sites was also sampled over the Southern Hemisphere summer (December–February) period. Five UV filters were detected with at least one detected in 95% of effluent samples. The summed concentration of UV filters ranged from 130 ng L−1 to 8400 ng L−1 and averaged 2800 (±1900) ng L−1. Of the target UV filters, 2-phenylbenzimidazole-5-sulfonic acid (PBSA) and benzophenone 4 (BP4) showed the lowest removal efficiencies (11 ± 36% and 51 ± 43%, respectively) across all sites and were the most abundant in effluent. Average estimated removal efficiencies of the other compounds were between 59 (±24) % (4-methylbenzylidene camphor (4-MBC)) and 74 (±22) % (benzophenone 1 (BP1)). We did not find a trend in seasonal differences in the per capita release of UV filters in effluent samples. We estimate that approximately 40% of UV filter loads measured in influent are breaking through to the effluent resulting in the release of approximately 20 kg day−1 of the selected UV filters into the aquatic environment from treated wastewater effluent in Australia.

Modeling the fate of UV filters in subsurface: Co-metabolic degradation and the role of biomass in sorption processes

Ultraviolet filters (UVFs) are emerging organic compounds found in most water systems. They are constituents of personal care products, as well as industrial ones. The concentration of UVFs in the water bodies in space and time is mostly determined by degradation and sorption, both processes being determinant of their bioavailability and toxicity to ecosystems and humans. UVFs are a wide group of compounds, with different sorption behavior expected depending on the individual chemical properties (pKa,Koc,Kow). The goal of this work is framed in the context of improving our understanding of the sorption processes of UVFs occurring in the aquifer; that is, to evaluate the role of biomass growth, solid organic matter (SOM) and redox conditions in the characterization of sorption of a set of UVFs. We constructed a conceptual and a numerical model to evaluate the fate of selected UV filters, focused on both sorption and degradation. The models were validated with published data by Liu et al. (2013), consisting in a suite of batch experiments evaluating the fate of a cocktail of UVs under different redox conditions. The compounds evaluated included ionic UV filters (Benzophenone-3; 2-(3-t-butyl-2-hydroxy-5-methylphenyl)5-chloro-benzotriazole; 2-(2′-hydroxy-5′-octylphenyl)-benzotriazole) and neutral ones (octyl 4-methoxycinnamatte; and octocrylene).

Chemometrics-Assisted Fast-Elution HPLC-DAD for the Quantification of Selected UV Filters and Parabens in Suncare Formulations.

In the present study, a fast LC method coupled with multivariate curve resolution (MCR) alternating least-squares (ALS) and alternating trilinear decomposition (ATLD) was developed for the determination of the resolution of and quantitation of benzophenone-3, 4-methylbenzylidene camphor, octocrylene, ethylhexyl dimethyl para-aminobenzoic acid, butyl methoxydibenzoilmethane, and methyl and propyl parabens in suncare products. Chromatographic separation was optimized using full factorial and Box-Behnken designs. MCR-ALS and ATLD performance in quantitating the analytes in synthetic mixtures (which were randomly prepared in ultra-pure water) and blank sunscreen products was studied, and satisfying results were obtained. Acceptable qualification and quantification results were also achieved in the presence of matrix interferences via a short chromatographic runtime (5 min), and the second-order advantage was fully exploited, with MCR-ALS clearly emerging as the superior model. Average recoveries ranged from 98.0 to 112.5%, and RSD values were lower than 6.5%. LODs between 0.066 and 0.243 μg/g were achieved. In addition to acceptable precision and accuracy, the merits of the proposed method are that the analysis is fast and there is minimal solvent consumption. Moreover, coelution of analytes and interference from components in the sample matrixes were overcome with multivariate analysis.

Environmental occurrence and risk of organic UV filters and stabilizers in multiple matrices in Norway

Eight organic UV filters and stabilizers were quantitatively determined in wastewater sludge and effluent, landfill leachate, sediments, and marine and freshwater biota. Crab, prawn and cod from Oslofjord, and perch, whitefish and burbot from Lake Mjøsa were selected in order to evaluate the potential for trophic accumulation. All of the cod livers analysed were contaminated with at least 1 UV filter, and a maximum concentration of almost 12μg/g wet weight for octocrylene (OC) was measured in one individual. 80% of the cod livers contained OC, and approximately 50% of cod liver and prawn samples contained benzophenone (BP3). Lower concentrations and detection frequencies were observed in freshwater species and the data of most interest is the 4 individual whitefish that contained both BP3 and ethylhexylmethoxycinnamate (EHMC) with maximum concentrations of almost 200ng/g wet weight. The data shows a difference in the loads of UV filters entering receiving water dependent on the extent of wastewater treatment. Primary screening alone is insufficient for the removal of selected UV filters (BP3, Padimate, EHMC, OC, UV-234, UV-327, UV-328, UV-329). Likely due in part to the hydrophobic nature of the majority of the UV filters studied, particulate loading and organic carbon content appear to be related to concentrations of UV filters in landfill leachate and an order of magnitude difference in these parameters correlates with an order of magnitude difference in the effluent concentrations of selected UV filters (Fig. 2). From the data, it is possible that under certain low flow conditions selected organic UV filters may pose a risk to surface waters but under the present conditions the risk is low, but some UV filters will potentially accumulate through the trophic food chain.

Simultaneous nitrification/denitrification and trace organic contaminant (TrOC) removal by an anoxic–aerobic membrane bioreactor (MBR)

Simultaneous nitrification/denitrification and trace organic contaminant (TrOC) removal during wastewater treatment by an integrated anoxic–aerobic MBR was examined. A set of 30 compounds was selected to represent TrOCs that occur ubiquitously in domestic wastewater. The system achieved over 95% total organic carbon (TOC) and over 80% total nitrogen (TN) removal. In addition, 21 of the 30 TrOCs investigated here were removed by over 90%. Low oxidation reduction potential (i.e., anoxic/anaerobic) regimes were conducive to moderate to high (50% to 90%) removal of nine TrOCs. These included four pharmaceuticals and personal care products (primidone, metronidazole, triclosan, and amitriptyline), one steroid hormone (17β-estradiol-17-acetate), one industrial chemical (4-tert-octylphenol) and all three selected UV filters (benzophenone, oxybenzone, and octocrylene). Internal recirculation between the anoxic and aerobic bioreactors was essential for anoxic removal of remaining TrOCs. A major role of the aerobic MBR for TOC, TN, and TrOC removal was observed.

Degradation of Six Selected Ultraviolet Filters in Aquifer Materials Under Various Redox Conditions

AbstractLaboratory biodegradation batch studies were performed to investigate the degradation behavior of six selected UV filters, namely benzophenone‐3 (BP‐3), 3‐(4‐methylbenzylidene) camphor (4‐MBC), Octyl 4‐methoxycinnamate (OMC), Octocrylene (OC), 2‐(3‐t‐butyl‐2‐hydroxy‐5‐methylphenyl)‐5‐chloro benzotriazole (UV‐326), and 2‐(2’‐hydroxy‐5’‐octylphenyl)‐benzotriazole (UV‐329) in an aquifer microcosm (groundwater and aquifer sediment mixture) under aerobic and anaerobic (nitrate, sulfate, and Fe(III) reducing) conditions within 77 d. The results from the biodegradation experiments showed that the six UV filters were degraded well in the aquifer materials under different redox conditions. Rapid biodegradation was observed for BP‐3 and OMC in the aquifer materials, with their half‐lives of 1.5‐8.8 d and 1.3‐5.2 d, respectively. In most cases, aerobic conditions were more favorable for the degradation of the UV filters in aquifer materials. Relatively slow degradation of 4‐MBC, UV‐326, and UV‐329 under anaerobic conditions was noted with their half‐lives ranging between 47 d and 126 d, indicating potential persistence in anaerobic aquifers. The results showed that redox conditions could have significant effects on biodegradation of the UV filters in aquifers.

DETERMINATION OF SUNSCREEN COMPOUNDS IN WATER SAMPLES BY SILICONE ROD EXTRACTION

Silicone rod extraction (SR) is a siloxane-based methodology for the extraction of organic pollutants from aqueous samples with similar principle extraction as the stir bar sorptive extraction (SBSE). In this study the SR was coupled with HPLC-DAD and employed for the extraction and quantification of selected UV filters in water and seawater samples. Chromatographic parameters were optimized as well as the main sorption/desorption conditions for 4-methylbenzylidene camphor (4MBC) and octyl-methoxy cinnamate (OMC) from both river water and seawater samples. After optimization of the proposed method the following variables were selected: 25,0 mL of sample volume, 3 hour extraction, 1250 rpm as stirring velocity and 2 mL methanol as desorption solvent. The recoveries from seawater samples were 76.6% for 4MBC and 85.9% OMC. In river water samples recoveries of 69.8% and 82.4 % for 4MBC and OMC, respectively, were observed when salt was added to the sample. Linear calibration curves were obtained in the corresponding matrix and quantification limits below 1.86 µg L -1 were obtained. A comparison between the proposed method and the SBSE alternative revealed that SR can be use as a reliably and cheap methodology for the determination of sunscreens.

Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in treated sewage sludge. The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography–tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g −1 dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g −1 dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved. The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4′-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g −1 dw.

Determination of selected UV filters in indoor dust by matrix solid-phase dispersion and gas chromatography–tandem mass spectrometry

A simple, inexpensive sample preparation procedure, based on the matrix solid-phase dispersion (MSPD) technique, for the determination of six UV filters: 2-ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (Homosalate, HMS), 3-(4-methylbenzylidene) camphor (4-MBC), isoamyl- p-methoxycinnamate (IAMC), 2-ethylhexyl- p-methoxycinnamate (EHMC) and octocrylene (OCR), in dust from indoor environments is presented and the influence of several operational parameters on the extraction performance discussed. Under the final working conditions, sieved samples (0.5 g) were mixed with the same amount of anhydrous sodium sulphate and dispersed with 2 g of octadecyl bonded silica (C18) in a mortar with a pestle. This blend was transferred to a polypropylene solid-phase extraction cartridge containing 2 g of activated silica, as the clean-up co-sorbent. The cartridge was first rinsed with 5 mL of n-hexane and the analytes were then recovered with 4 mL of acetonitrile. This extract was adjusted to 1 mL, filtered and the compounds were determined by gas chromatography combined with tandem mass spectrometry (GC–MS/MS). Recoveries for samples spiked at two different concentrations ranged between 77% and 99%, and the limits of quantification (LOQs) of the method between 10 and 40 ng g −1. Analysis of settled dust from different indoor areas, including private flats, public buildings and vehicle cabins, showed that EHMC and OCR were ubiquitous in this matrix, with maximum concentrations of 15 and 41 μg g −1, respectively. Both UV filters were also quantified in dust reference material SRM 2585 for first time. EHS, 4-MBC and IAMC were detected in some of the analyzed samples, although at lower concentrations than EHMC and OCR.

Occurrence and behavior of four of the most used sunscreen UV filters in a wastewater reclamation plant

Four UV filters, benzophenone-3 (BP-3), 4-methylbenzylidence camphor (4-MBC), ethylhexyl methoxycinnamate (EHMC), and octocrylene (OC), have been examined along the different units of a wastewater reclamation plant (WWRP) located in Tianjin, North China. The analytical procedure included solid-phase extraction and gas chromatographic/mass spectrometric analyses. All four UV filters were detected in the influent during the three sampling campaigns (February, July, and September), and the concentrations ranged from 34 to 2128 ng L −1. The concentrations of the four UV filters were higher in hot weather (July and September) than in cool weather (February). The monthly average removal ranged from 7.6% to 21% for the selected UV filters during coagulation–flocculation (C–F) treatment. The ozonation treatment achieved the maximum removal (16–28%); on the contrary, the continuous microfiltration (CMF) achieved the lowest removal (3.6–8.2%). The total removal efficiencies along the plant varied from 28% to 43%. These results indicate that the UV filters are not completely removed during WWRP treatment and may be carried over into the environment during the reuse applications.