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Occurrence and fate of benzophenone-type UV filters in aquatic environments: A review
Abstract
Benzophenone-type ultraviolet filters (BP-type UV filters or BPs) are extensively used in a diverse array of personal care products (PCPs), including sunscreens and many cosmetics. The widespread use of BPs has resulted in their release into aquatic environments, directly via human recreational activities and indirectly via effluents of wastewater treatment plants (WWTPs). BPs have been reported to elicit endocrine disrupting properties. This paper reviews the knowledge regarding the physicochemical properties, occurrence, fate and behavior of BPs in aquatic environments. Despite high removal efficiency in WWTPs, BPs are consistently detected in effluents at relatively low concentrations. Although BPs readily undergo biodegradation and indirect photolysis, they are considered to be pseudo-persistent in surface waters and benthic sediments, a result of usage of BP-contained products and continuous release into the environment. In the BP family, benzophenone-3 (BP-3) is the dominant species in the environment, possibly a reflection of the composition of BPs in commercial and industrial products. BPs can react rapidly with aqueous chlorine, forming halogenated by-products. Knowledge on the occurrence, fate and toxicity of these halogenated by-products is scarce and needs further investigation.
... Benzophenones are also synthesised by humans because of their ability to absorb ultraviolet (UV) radiation, for which these substances are exploited in various branches of industry (28). Benzophenones are used in the production of sunscreens, cosmetics, personal care products, inks, paints and other products that need to resist sunlight degradation (21,44,45,64). They are also present in food containers, plastic bottles, clothes and perfumes. ...
... The results obtained have confirmed that dogs are exposed to benzophenones. It is related to the common use of BPs in various branches of industry and the resultant extensive pollution of the environment (26,34,44,45), and to dogs' exposure to the same toxic factors as their owners, being companion animals living in close proximity to humans. The present study has shown that dogs are exposed to BP-3 to the greatest extent, which was found in all samples included in the study. ...
... The present study has shown that dogs are exposed to BP-3 to the greatest extent, which was found in all samples included in the study. It agrees with previous studies, which have shown that BP-3 is the benzophenone that pollutes the natural environment most often and in the largest quantities and one which occurs in living organisms (26,44,45). The present study has also revealed the second most common BP in dogs to be BP-1. ...
Introduction
Benzophenones (BPs) are used in various branches of industry as ultraviolet radiation filters, but they pollute the natural environment, penetrate living organisms, and disrupt endocrine balance. Knowledge of the exposure of domestic animals to these substances is extremely scant. The aim of the study was to investigate long-term exposure of companion dogs to BPs and relate this to environmental factors.
Material and Methods
Hair samples taken from 50 dogs and 50 bitches from under 2 to over 10 years old were analysed for BP content with liquid chromatography–tandem mass spectrometry.
Results
The results revealed that dogs are most often exposed to 2-hydroxy-4-methoxybenzophenone (BP-3) and 4-dihydroxybenzophenone (BP-1). Concentration levels of BP-3 above the method quantification limit (MQL) were noted in 100% of the samples and fluctuated from 4.75 ng/g to 1,765 ng/g. In turn, concentration levels of BP-1 above the MQL were noted in 37% of the samples and ranged from <0.50 ng/g to 666 ng/g. Various factors (such as the use of hygiene and care products and the dog’s diet) were found to affect BP concentration levels. Higher levels of BP-3 were observed in castrated/spayed animals and in animals that required veterinary intervention more often.
Conclusion
The results obtained show that the analysis of hair samples may be a useful matrix for biomonitoring BPs in dogs, and that these substances may be toxic to them.
... The model cannot reproduce redox conditions, which would require multiple immobile zones (the most reducing conditions are reached in the least accessible portions of the medium). Therefore, a simplified degradation network, using only the analyzed species and neglecting redox state, has been adopted 25,38,39 (Figure 2c). This network is further discussed in Section 3.2. ...
... This transformation pathway can occur both in oxic and anoxic conditions. 25 Note that BP-1 was also present in the influent water ( Figure 3, blue shadow zone), meaning it was already present in the inlet water of the WWTP or it was formed there, as observed in Mao et al. 39 After the injection of LiAc, BP-1 dropped in the ST and remained below the method limit of detection at the CT. BP-1 biodegradation can lead to the formation of 4DHB. ...
... Finally, 4HB can be formed from 4DHB or, directly, from BP-1 by a hydroxyl group loss 39 (Figure 2c). Interestingly, this compound was not present in the inflow water. ...
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.
... Organic UV absorbents (UVAs), including UV filters (UVFs) and benzotriazole UV stabilizers (BZT-UVs), are contaminants of emerging concern. They are widely used in personal care products (e.g., sunscreens), cosmetics, plastics, paints, automobile polymeric components, varnishes, and many others to protect human skin from sunburn or prevent industrial and commercial products from sunlight induced degradation and color change of materials (Mao et al., 2019;Nakata et al., 2009). ...
... Determining whether the samples from these sites share any distinguishing characteristics that could explain the elevated BP3 levels is crucial. For example, fish from sites close to local contamination sources (e.g., wastewater treatment plants) may have higher exposure to BP3 (Castilloux et al., 2022;Mao et al., 2019). These factors require additional analysis and consideration to completely elucidate the spatial patterns of BP3 and their environmental implications. ...
... BP3 has been detected in wild marine fish samples worldwide, and its endocrine-disrupting properties in organisms are of environmental concern (Cuccaro et al., 2022). The distribution and level of BP3 vary greatly depending on different factors such as geographic area, fish species and tissue analyzed (Mao et al., 2019). When compared to previously reported findings in marine fish from various places, the BP3 levels detected in the muscle of small redfish in the present study tend to be greater ( Table 2). ...
... Seasonal variations in the environment can depend on physical (e.g., varying flow patterns and stratification), chemical (photolysis) (Batchu et al., 2014;Blum et al., 2017;Dodson et al., 2011;Trawiński and Skibiński, 2019) and biological (biodegradation) (Baena-Nogueras et al., 2017) factors. In lake systems, temporal variations can occur due to e.g., recreational activities and usage patterns of certain CECs (Mao et al., 2019), or to variations in photodegradation between seasons (Bonvin et al., 2011;Lindholm-Lehto et al., 2016). Spatial variations in lake systems can occur depending on proximity to large-scale WWTPs and WWTP treatment efficiency , or other pollution sources, e.g., landfill leachate . ...
... A Friedman test followed by a Tukey-Kramer post hoc test was performed for sites L1, L7, and L8 to evaluate seasonal variations at sites close to urban areas (viz. Fig. 1), using data for four seasons (Fig. 4) Seasonal variations have been reported previously for PCPs (UV-filters) (reviewed by Mao et al., 2019), parabens (reviewed by Haman et al., 2015), antihistamines , and antibiotics (Moreno-González et al., 2014). To our knowledge, seasonal variations have not been reported previously for antidiabetics and antineoplastics. ...
... Seasonal variations in concentrations of benzophenone-type UV-filters in river water are known, and their lower mass loads in spring could be due to their use in other PCPs (Mao et al., 2019). Clozapine degrades under direct photolysis (Trawiński and Skibiński, 2019). ...
Contaminants of emerging concern (CECs) is one of several reasons for the deterioration of surface water quality globally, even though the CECs occur in trace concentrations. This thesis produced new CEC data through a oneyear field study for substances which occur in Sweden’s three largest lakes and their associated rivers. The purpose was to investigate mass flows and seasonal variations of CECs, as well as estimate the potential ecotoxicological hazard posed by the CECs’ occurrence. It was found that numerous CECs occurred in all examined rivers, and that a continuous influx of CECs with suspected hazardous properties into the lakes occurred. Total mass loads of the investigated CECs were estimated from 0.51 to 5.6 kg/day in the influx to the lakes, and from 0.12 to 4.3 kg/day in the outflux from the lakes. Seasonal variations were observed in the aquatic environment for both individual and groups of CECs. This could be due to variations in consumption and environmental conditions. Some of the seasonal variations were being reported for the first time in the academic literature. Many of the CECs were suspected to have the combination of the hazardous properties of persistency, mobility, and toxicity (PMT). Of the 71 CECs detected far from any suspected input into the lakes, 20 had previously been suspected of having PMT properties. Within the remaining 51 CECs, multiple others also had suspected PMT properties. The thesis suggests that CECs with suspected PMT properties should be analysed closer with respect to these properties.
... One of these ingredients is benzophenone-3 (BP-3), which is found in several personal care products such as sunscreen, lotions, conditioners, and cosmetics because it absorbs and disperses ultraviolet (UV) rays and provides protection against the harmful effects of UV radiation. [1][2][3] However, the increased production and widespread use of BP-3 has resulted in the increased release of BP-3 into aquatic environments. [2] The occurrence of BP-3 in the aquatic environment has been reported in rivers (2 µg L −1 ), [4] lakes (up to 0.5 µg L −1 ), [5] and beaches (up to 5.4 µg L −1 ). ...
... [1][2][3] However, the increased production and widespread use of BP-3 has resulted in the increased release of BP-3 into aquatic environments. [2] The occurrence of BP-3 in the aquatic environment has been reported in rivers (2 µg L −1 ), [4] lakes (up to 0.5 µg L −1 ), [5] and beaches (up to 5.4 µg L −1 ). [6] However, the highest BP-3 concentrations were detected predominantly in tourist areas. ...
... [11] These compounds, when released into the environment, rapidly accumulate in aquatic organisms such as coral, crustaceans, mussels, and fish. [2,[12][13][14][15][16][17][18] Moreira and Luchiari [19] reported that adult zebrafish (Danio rerio) that were exposed to concentrations of 10, 100, and 1,000 μg L −1 BP-3 exhibited reduced locomotion and decreased interaction time with other fish. In addition, it caused adverse environmental effects including negative health effects (bleaching and enhanced mortality) on coral reefs and harmful hormonal effects on the marine fauna. ...
Benzophenone (BP-3) is an organic compound that is a common ingredient in lotions, conditioners, and other personal care products, which helps protect against ultraviolet radiation. This study investigated the effect of BP-3 on the structure of the integument and gills, as well as the activities of superoxide dismutase (SOD) and catalase (CAT) in the gills of Danio rerio. Fish were exposed to different concentrations (7, 70, and 700 µg L −1) of BP-3 for 7 and 14 d. For the histological analysis of the integument and gills, the fish were fixed in Bouin liquid and processed according to standard histologic procedures, and the tissue section slices were stained according to different histochemical methods. BP-3 caused tissue damage and morphological alterations in the gills; however, the integument showed no histological or morphological alterations. Furthermore, there was no observed correlation between the BP-3 concentration and exposure period and the gill alterations, as these did not occur in a linear manner. The gills were removed to evaluate the antioxidant defense; for this, CAT and SOD activities were measured, and a reduction of SOD activity was noted, whereas the CAT activity was not significantly affected.
... Two main pathways have been identified for these chemicals to enter the aquatic environment. Substantial amounts of these chemicals are released directly [15]. Another important source is discharge via wastewater treatment plants (WWTPs) [15]. ...
... Substantial amounts of these chemicals are released directly [15]. Another important source is discharge via wastewater treatment plants (WWTPs) [15]. In both cases, the release into the aquatic environment is a result of the use of cosmetics, showering, washing, rubbing off and excretion after dermal application during recreational activities such as sunbathing and swimming. ...
... Thus, one part of them focusses on the analytical methodologies applied for the determination of organic UV filters achieved by mass spectrometric-based gas or liquid chromatography [3,6,8,16]. Another considerable portion of the reviews focusses on their occurrence, fate and distribution in biological and environmental samples (e.g., water, soil, sediments, sludge and biota) [2,7,12,15,17]. Among aquatic ecosystems, occurrence and distribution of organic UV filters in marine environment [2,6] have also been reviewed. ...
Present review discusses current trends in the gas chromatographic-mass spectrometric (GC-MS) determination of sixteen organic UV filters belonging to the classes of i) benzophenones (BPs); and ii) salicylate and benzoate esters added to sunscreens due to their excellent UV absorbing properties covering both UVA and UVB ranges. Possibilities for identification and quantitation of organic UV filters with or without derivatization are, hereby, presented. Concerning derivatization, conditions for application of alkyl silylation with N,O-bis(Trimethylsilyl)trifluoroacetamide (BSTFA), N-Methyl-N- (trimethylsilyl)trifluoroacetamide (MSTFA) and N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) have been compiled. In the past 17 years, derivatization was applied in 36% of the about 121 peer reviewed articles included in the present report, silylation being the most popular approach (cca. 90%). However, not so widespread derivatization approaches such as acetylation with acetic acid anhydride (Ac2O) and oximation with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA) are also discussed. According to their frequency of use, these derivatization reagents are ranked as follows: BSTFA > MSTFA > MTBSTFA > Ac2O > PFBHA. The organic UV filters that can only be determined by derivatization are hydroxylated derivatives of BP such as benzhydrol, 2,4-dihydroxybenzophenone (BP1), 2,2′,4,4′-tetrahydroxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2-hydroxy-benzophenone, 3-hydroxy-benzophenone, 4-hydroxy-benzophenone and 2,3,4-trihydroxy-benzophenone. To the contrary, the GC-MS determination of BP is achieved: i) directly; ii) directly together with its hydroxyl derivatives after silylation or acylation; iii) after derivatization with PFBHA. Trends in determination of these analytes in environmental compartments (e.g., water, sediment) and biota are also discussed. The most frequently studied BPs in these samples are 2-hydroxy-4-methoxy-benzophenone or oxybenzone (BP3) > BP1 ≅ BP.
... They also demonstrate high stability; for example, in surface waters, the half-life of oxybenzone is reported to be ~2.4 years [12,13]. BPs have been widely used because of their ultraviolet (UV)-absorbing properties, finding application as UV filters in sunscreens, cosmetics, and personal care products. ...
... Their occurrence in the environment depends on the way that they enter and the frequency of use. In the case of BPs, their existence is mainly due to use in consumer products and inefficient treatment of wastewater in treatment plants [3,6,13]. Their transport to the environment depends strongly, as in the case of all chemical stressors in environmental media, on their physicochemical characteristics [13]. ...
... In the case of BPs, their existence is mainly due to use in consumer products and inefficient treatment of wastewater in treatment plants [3,6,13]. Their transport to the environment depends strongly, as in the case of all chemical stressors in environmental media, on their physicochemical characteristics [13]. As previously mentioned, BPs are lipophilic molecules with a wide range of octanol/water partition coefficients (LogPow) [21] and a wide range of organic carbon partition coefficients (Koc), exhibiting medium to high solubility in water [13,22]. ...
The ubiquitous presence of emerging contaminants in the environment is an issue of great concern. Notably, for some of them, no established regulation exists. Benzophenones are listed as emerging contaminants, which have been identified in the environment as well as in human fluids, such as urine, placenta, and breast milk. Their accumulation and stability in the environment, combined with the revealed adverse effects on ecosystems including endocrine, reproductive, and other disorders, have triggered significant interest for research. Benzophenones should be extracted from environmental samples and determined for environmental-monitoring purposes to assess their presence and possible dangers. Numerous sample preparation methods for benzophenones in environmental matrices and industrial effluents have been proposed and their detection in more complex matrices, such as fish and sludges, has also been reported. These methods range from classical to more state-of-the-art methods, such as solid-phase extraction, dispersive SPE, LLE, SBSE, etc., and the analysis is mostly completed with liquid chromatography, using several detection modes. This review critically outlines sample preparation methods that have been proposed to date, for the extraction of benzophenones from simple and complex environmental matrices and for cleaning up sample extracts to eliminate potential interfering components that coexist therein. Moreover, it provides a brief overview of their occurrence, fate, and toxicity.
... Studies have reported the accumulation of UV filtering substances in tissues of aquatic organisms (Blüthgen et al., 2014;Pawlowski et al., 2019;Wang et al., 2022). Seasonal variation in use and release of UV filters, with higher concentrations in summer, may have consequences for aquatic organisms via the potential for reproductive and developmental toxicity (Cunha et al., 2022;Ma et al., 2023;Mao et al., 2019;Ramos et al., 2016;Wang et al., 2023). ...
... The behavior and fate of sunscreen compounds in the environment have been recently investigated (Hu et al., 2021;Magi et al., 2013;Mao et al., 2019). The organic UV filters they contain cannot be completely removed via WWTP and enter water bodies throughout the year (Ekpeghere et al., 2016;Ramos et al., 2016). ...
Personal care products, including organic UV filters, are considered emerging contaminants, with their toxic effects being a concern in recent decades. UV filters continually enter surface waters via wastewater and human activity. Despite the presence of organic UV filters in the freshwater environment, little is known of their impact on aquatic biota. In this study, we evaluated the cardiac and locomotor responses of signal crayfish Pacifastacus leniusculus exposed to environmentally relevant concentrations of either 2-Phenylbenzimidazole-5-sulfonic acid (PBSA, 3 µg/L) or 5-Benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (BP4, 2.5 µg/L). Specimens exposed to the tested compounds for 30 min exhibited significantly greater changes in distance moved and time active than did unexposed controls. Significant differences of mean heart rate change compared to control were detected in both PBSA and BP4 experimental groups. Such behavior and physiological alterations demonstrate ecological effects of personal care products with the tested sunscreen compounds even with a short exposure. Evidence of the consequences of organic UV filters on aquatic organisms is scarce and is an important topic for future research.
... As per the European Union Cosmetics Directive, the register of commercial cosmetic products includes 28 UV filters approved for use as active elements in cosmetics [4]. These UV filters encompass benzophenones, such as 2-hydroxy-4-methoxy-benzophenone (BP-3), 2,4-dihydroxybenzophenone (BP-1), 2,2 ′ ,4,4 ′ -tetrahydroxybenzophenone (BP-2), 2,2 ′dihydroxy-4-methoxy-benzophenone (BP-8), 2-hydroxy-4-methoxy-4 ′ -methyl-benzophenone (BP-10), 4-hydroxybenzophenone (4HBP), and 2,3,4-trihydroxybenzophenone (234HBP); derivatives of salicylate include ethyl hexyl salicylate (EHS), benzyl salicylate (BS), and homosalate (HS), which are some of the most common UVFs used in commercial products [5,6]. UVFs can enter the aquatic environment through multiple pathways, including indirect routes like the release of effluents from wastewater treatment plants into natural water bodies, as well as direct routes from recreational activities. ...
Organic sun-blocking agents are recognized as emerging pollutants of the aquatic environment. The consequences and effects of these harmful substances on aquatic organisms are not fully understood, particularly in the context of Romania. This study examines the presence and environmental hazards posed by ten UV filters found in the Danube River. Six of the ten targeted contaminants were detected in surface water samples: 2-hydroxy-4-methoxy-benzophenone (BP-3), 2,4-dihydroxy benzophenone (BP-1), 2,3,4-trihydroxy benzophenone (234HBP), 2,2′-dihydroxy-4-methoxy-benzophenone (BP-8), 2-hydroxy-4-methoxy-4′-methyl-benzophenone (BP-10), and benzyl salicylate (BS). In sediment samples, seven of the ten compounds were identified: BS, BP-3, 4-hydroxybenzophenone (4HBP), BP-1, 234HBP, 2,2′,4,4′-tetrahydroxybenzophenone (BP-2), and BP-10, with different frequencies. The correlation coefficients showed strong relationships between benzophenone derivatives in surface water samples and a common contamination source for BP-3 and BS in sediment samples. In the assessment, the risk quotient (RQ) for BP-1 in fish was determined to be 1.81. Similarly, RQ values for BP-3 were calculated as 1.24 for Daphnia magna and 57 for fish, suggesting that these UV filters could potentially present substantial hazards to the aquatic ecosystem. The study findings indicate that additional research is needed to investigate the presence and potential risks of organic sun-blocking agents in surface waters, with a particular emphasis on densely populated areas in Romania.
... Recently, researchers have modified and altered the molecular backbone of benzophenone using 2, 4-dihydroxybenzophenone (UV-0) as raw material. [13][14][15] Dietrich Braun et al [16] produced terpolymer stabilizers with higher UV absorption efficiency and lower mobility compared to low molecular weight UV absorber monomers. Liang et al [17] synthesized a novel low surface energy fluorinated UV absorber. ...
In this work, two new functionalized monosubstituted and disubstituted benzophenone derivatives have been synthesized through a one‐step nucleophilic substitution treatment using dihydroxybenzophenone and arylsulfonyl chloride as raw materials. All the compounds were characterization by NMR and MS spectroscopy technology and the resulting products exhibited efficient UV light absorption in the range of 220–350 nm. The monosubstituted products can effectively improve the photostability of light‐curable coatings and extend the storage time of coatings, the disubstituted one as photoinitiators possess fantastic photoinitiation effect, and the cured coating is smooth and transparent with good adhesion. The introduction of benzenesulfonyl groups on the skeleton of dihydroxybenzophenone(UV‐0) can enhance the compatibility of the compounds with monomers and active diluents, and also improve the defects of yellowing and small molecule migration of cured products. Among them, the monosubstituted products as UV absorber can effectively improve the photostability of the photocurable coating and extend the storage time of coating. As a photoinitiator, the disubstituted products have good photoinitiation effect, and the cured coating are smooth and transparent, and good adhesion.
... Based on the E int and E ad values, it was observed that the most favorable adsorption sequence for the formed GO-BPs complexes are GO-BP-2 > GO-BP-3 > GO-BP-1 (Table 3). Apparently, BP2 pollutants that are less soluble in water (0.5-1 mg/L) are more likely to adsorb onto the GO surface than BP1 or BP3 under the same conditions owing to the fact they have fewer opportunities to remain in solution and are more likely to come into contact with the solid surface [23]. For instance, after undergoing geometrical optimization, a favorable adsorption interaction was induced between the oxygen atom of the pollutants and hydrogen atom number 47 of GO, resulting in a decrease in their distance from 2.72 to 1.54 Å as evident from the data presented in Table 1. ...
In this study, we investigate the adsorption behavior of three benzophenone derivatives, namely 2,4-Dihydroxybenzophenone (benzophenone-1; BP-1), 2,2′,4,4′-tetrahydroxybenzophenone (benzophenone-2; BP-2), and 2-hydroxy-4-methoxybenzophenone (benzophenone-3; BP-3) on the surfaces of graphene oxide (GO) using density functional theory method. The geometric optimization of the unaltered structures of GO adsorbent, benzophenone derivatives, and their respective complexes was conducted via the M052X/6-311 + G* level of theory. The optimal temperature for the interaction between the GO adsorbent and BPs pollutants in the aqueous phase was found to be 298.15 K. The adsorption process was found to be spontaneous, exothermic, and irreversible based on the calculated values of adsorption energy, Gibbs free energy (ΔGad), and enthalpy (ΔHad). The negative values of the calculated chemical potential for all structures indicated that the studied structures were thermodynamically stable. The adsorption of BP-2 pollutant on the surface of GO results in a highest dipole moment (μd = 28.22 D) compared to the corresponding unadsorbed molecule (μd = 7.93 D). The adsorption efficiency of GO–BPs complexes follows an increasing trend of GO–BP-2 (−1009.75 kcal/mol) > GO–BP-3 (−1006.31 kcal/mol) > GO–BP-1(−1000.65 kcal/mol). Moreover, infrared (IR) frequency calculations confirmed the feasibility of the structures, showing true local minima. The recovery time values indicate that GO is a highly effective adsorbent in removing organic BP-2 pollutants (\(\tau =\) 3.158 ms) from aqueous media rather than BP-3 (\(\tau =\) 2.120 ms) and BP-1 (\(\tau =\) 1.831 ms) counterparts. Other key parameters engaged in the adsorption behavior of considered molecules, including charge capacity, electrophilicity, band gap, chemical potential, and chemical hardness, were also deliberated.
... The occurrence and fate of BPs in aquatic environments, coupled with their consequential impact on aquatic ecosystems, have garnered significant attention [24,57]. Notably, attention was drawn to the risks associated with organic UV filters in marine and freshwater environments [58]. ...
Benzophenone ultraviolet light filters (BPs) are high-production-volume chemicals extensively used in personal care products, leading to widespread human exposure. Given their estrogenic properties, the potential health risks associated with exposure to BPs have become a public health concern. This review aims to summarize sources and pathways of exposure to BPs and associated health risks. Dermal exposure, primarily through the use of sunscreens, constitutes a major pathway for BP exposure. At a recommended application rate, dermal exposure of BP-3 via the application of sunscreens may reach or exceed the suggested reference dose. Other exposure pathways to BPs, such as drinking water, seafood, and packaged foods, contribute minimal to the overall dose. Inhalation is a minor pathway of exposure; however, its contribution cannot be ignored. Human exposure to BPs is an order of magnitude higher in North America than in Asia and Europe. Studies conducted on laboratory animals and cells have consistently demonstrated the toxic effects of BP exposure. BPs are estrogenic and elicit reproductive and developmental toxicities. Furthermore, neurotoxicity, hepatotoxicity, nephrotoxicity, and carcinogenicity have been reported from chronic BP exposure. In addition to animal and cell studies, epidemiological investigations have identified associations between BPs and couples' fecundity and other reproductive disorders, as well as adverse birth outcomes. Further studies are urgently needed to understand the risks posed by BPs on human health.
... It is estimated that around 25% of sunscreen applied to the skin is washed off in a single bath [5,6]. Indirect sources of UV filters are insufficiently treated effluents from wastewater treatment plants (WWTPs) [7][8][9]. BP-1 (benzophenone-1), BP-2 (benzophenone-2), BP-3 (benzophenone-3), 4-MBC. ...
UV filters in environmental compartments are a source of concern related to their ecotoxicological effects. However, little is known about UV filters’ toxicity, particularly those released into the environment as mixtures. Acute toxicity of nine organic UV filters benzophenone-1, benzophenone-2, benzophenone-3, 4-methoxy benzylidene camphor, octocrylene, ethylhexyl methoxycinnamate, 2-ethylhexyl salicylate, homosalate, and butyl methoxydibenzoylmethane was determined. UV filter solutions were tested as single, binary, and ternary mixtures of various compositions. Single solutions were tested using a set of bio tests, including tests on saline crustaceans (Artemia franciscana), freshwater crustaceans (Daphnia magna), marine bacteria (Aliivibrio fischeri), and freshwater plants (Lemna minor). The tests represent different stages of the trophic chain, and hence their overall results could be used to risk assessment concerning various water reservoirs. The toxicity of binary and ternary mixtures was analyzed using the standardized Microtox® method. Generally, organic UV filters were classified as acutely toxic. Octocrylene was the most toxic for Arthemia franciscana (LC50 = 0.55 mg L–1) and Daphnia magna (EC50 = 2.66–3.67 mg L–1). The most toxic against freshwater plants were homosalate (IC50 = 1.46 mg L–1) and octocrylene (IC50 = 1.95 mg L–1). Ethylhexyl methoxycinnamate (EC50 = 1.38–2.16 mg L–1) was the most toxic for marine bacteria. The least toxic for crustaceans and plants were benzophenone-1 (EC50 = 6.15–46.78 mg L–1) and benzophenone-2 (EC50 = 14.15–54.30 mg L–1), while 4-methoxy benzylidene camphor was the least toxic for marine bacteria (EC50 = 12.97–15.44 mg L–1). Individual species differ in their sensitivity to the tested organic UV filters. An assessment of the toxicity of mixtures indicates high and acute toxicity to marine bacteria after exposition to a binary mixture of benzophenone-2 with octocrylene, 2-ethylhexyl salicylate, or homosalate. The toxicity of mixtures was lower than single solutions predicting antagonistic interaction between chemicals.
Graphical abstract
... The benzophenone family is one of the most frequently used group, not only in PCPs, but also in several industrial products; thereby, they are highly detected in marine organisms (Mao et al., 2019;Tsui et al., 2017). However, although several benzophenone derivative by-products can be found in the environment (more than 17, including metabolites and hydroxylated forms) (Carve et al., 2021), their bioaccumulation has been only observed for five of them, with BP3 being the most detected one. ...
... At the same time, BPs can also be brought into water through water entertainment activities such as swimming and bathing [1]. BPs have been detected in various water samples [2] and other environmental media [3,4]. Furthermore, BPs can also enter the human body through the skin, diet and air, which poses a threat to human health. ...
This work demonstrates the potential utility of ferrate(VI)-based advanced oxidation processes for the degradation of a representative UV filter, BP-4. The operational parameters of oxidant dose and temperature were determined with kinetic experiments. In addition, the effects of water constituents including anions (Cl−, HCO3−, NO3−, SO42−), cations (Na+, K+, Ca2+, Mg2+, Cu2+, Fe3+), and humic acid (HA) were investigated. Results suggested that the removal rate of BP-4 (5 mg/L) could reach 95% in 60 min, when [Fe(VI)]:[BP-4] = 100:1, T = 25 °C and pH = 7.0, The presence of K+, Cu2+ and Fe3+ could promote the removal of BP-4, but Cl−, SO42−, NO3−, HA and Na+ could significantly inhibit the removal of BP-4. Furthermore, this Fe(VI) oxidation processes has good feasibility in real water samples. These results may provide useful information for the environmental elimination of benzophenone-type UV filters by Fe(VI).
... In recent decades, there has been an increase in the use of oxybenzone-containing PCPs, which has led to a considerable accumulation of oxybenzone in soil, groundwater, and aquatic environments (Manasfi et al. 2017). Owing to the limitations and ineffectiveness of sewage treatment technologies, a large amount of oxybenzone enters the soil environment (Gago-Ferrero et al. 2011;Mao et al. 2019;Zhong et al. 2020a). The oxybenzone concentration in soil samples has increased to approximately 26.7 mg•kg −1 , which could result in significant adverse effects on crop yield and agricultural ecosystem (Gautam et al. 2022;Li et al. 2022;Sunyer-Caldu and Diaz-Cruz 2021;Zhong et al. 2020a). ...
Purpose
Oxybenzone has received widespread attention owing to its extensive accumulation in the soil and adverse effects on plant growth. The aim of the study was to verify the potential of tobacco (Nicotiana tabacum) combined with the use of adenine and plant growth-promoting rhizobacteria (PGPR) (Methylophilus sp. strain FP-6) to enhance the efficiency of oxybenzone removal from the soil, and investigate the interaction between adenine and strain FP-6 that occurred during the phytoremediation process.
Methods
First, we determined whether the presence of adenine stimulated the growth and plant growth-promoting (PGP) traits of strain FP-6, which was isolated in our previous study and demonstrated considerable potential for the degradation of oxybenzone. The combined effects of strain FP-6 and adenine on the growth of tobacco and the efficiency of oxybenzone removal from the soil were then investigated. Furthermore, we evaluated the soil enzyme activities and microbial community composition in tobacco-growing soil containing oxybenzone.
Results
The adenine-FP6 amendment significantly improved photosynthetic efficiency and maintained the ion homeostasis of tobacco, which was destroyed by oxybenzone, thereby promoting the efficiency of phytoremediation of oxybenzone by tobacco (97.99%). Furthermore, a series of hydrolases involved in nutrient cycles and oxidoreductases with high reactivity to phenolic compounds in the soil were significantly up-regulated under this remediation strategy, which might be attributed to the increased relative abundance of some rhizosphere bacteria, such as Faecalibacterium, Agathobacter, and Sphingomonas.
Conclusion
The findings of this study provide an economical and ecological phytoremediation strategy for the efficient remediation of oxybenzone -contaminated soils.
... The detection of these CEC at trace-levels, specifically benzophenone-3 (BP-3), fipronil (FIP) and propylparaben (PPB) has also increased [2][3][4][5][6]. BP-3 was detected in outdoor swimming pool water [7,8] and surface water [9] at concentration levels up to hundreds of ng L − 1 . FIP was detected in concentrations that exceed established reference value to preserve aquatic life c.a. (11 ng L − 1 ) by 46 % in California surface waters [148], 70 % in U.S. streams and rivers [149], and by >20 % in agricultural multi-use streams in the USA [149]. ...
Benzophenone-3 (BP-3), fipronil (FIP) and propylparaben (PPB), are chemical compounds classified as contaminants of emerging concern (CEC) and known as refractory to natural biological degradation and conventional water treatments. Their occurrence in aqueous matrices is threatening to ecosystems, making it necessary to implement efficient technologies for their elimination from these matrices. Advanced oxidation processes (AOPs) have been suggested as complementary tertiary treatments in municipal wastewater treatment plants aiming at CEC degradation. This review provides a timely overview of different AOPs reported for BP-3, FIP and PPB degradation to give a complete picture of current knowledge regarding their removal from aqueous matrices. Recent progresses on circumventing negative effects of operational parameters were also surveyed and contrasted. The involvement of Green Chemistry (more exactly, Sustainable Chemistry) practices in these processes, evidenced by the use of red mud for persulfate activation, is an important step forward. However, low degradation rates (~48 %) achieved in real matrices continue to be a challenge for AOPs performance in real scale. In addition, published studies point out to successful degradation of target-CEC with the formation of less toxic transformation products for BP-3 and PPB. Finally, the current status of these processes regarding new developments and applications of AOPs is presented along with merits and limitations.
... The maximum concentration of BP-3 in sunscreen products allowed by the United States Food and Drug Administration (FDA) is 6%. 2 The widespread application of BP UV filters in personal care products (PCPs) has resulted in their ubiquitous occurrence in aquatic environment. 3 There is a growing concern about health risks from BP exposure because of their estrogenic properties. 4,5 Humans are exposed to BPs mainly through dermal absorption from the use of sunscreen and other PCPs (e.g., skin lotions). ...
Benzophenone (BP)-type ultraviolet (UV) filters are estrogenic chemicals used extensively in sunscreen products, leading to concerns over human exposure. To assess exposure to BP derivatives in sunscreens, we tested 14 BP UV filters in 50 products representing 44 brands marketed in the United States in 2021, finding BP, 2-hydroxy-4-methoxybenzophenone (BP-3 or oxybenzone), 2,2'-dihydroxy-4-methoxybenzophenone (BP-8), 2-hydroxy-4-methoxy-4'-methylbenzophenone (BP-10), 2,3,4-trihydroxybenzophenone (2,3,4-OH-BP), and 4-methylbenzophenone (4-Me-BP) in ≥70% of the samples. The geometric mean (GM) concentration of the sum of these BPs (∑14BPs) in the 50 products was 6600 ng/g. BP-3 was the predominant BP in oxybenzone-containing products (accounting for >99% of the total concentration), with a concentration 5-6 orders of magnitude higher than that in "oxybenzone-free" products (GM: 35 600 000 vs 113 ng/g). BP was present in >90% of products analyzed, including those labeled "oxybenzone-free" (GM: 2100 ng/g). BP concentrations were ∼100-fold higher in octocrylene-containing vs "octocrylene-free" products (GM: 15900 vs 151 ng/g). Dermal exposure doses of BP-3 from oxybenzone-containing products (GM: 4140 000 ng/kg body weight (BW)/day) and of BP in some (24%) octocrylene-containing products (GM: 12 200 ng/kg BW/day) were above reference values (2 000 000 and 30 000 ng/kg BW/day for BP-3 and BP, respectively). This study provides evidence that BP and BP-3 concentrations in sunscreen products vary widely and may be noteworthy even in products labeled oxybenzone- or octocrylene-free, making dermal exposure a continuing concern.
... BPs enter the aquatic environments either by direct input of outdoor swimmers or by indirect input of the effluent discharge from wastewater treatment plants (WWTPs) (Kim and Choi, 2014). The occurrences of BPs are reported in varying levels depending on the intensities of daily use and discharge ranging from ng L − 1 in surface water to μg L − 1 in wastewater, swimming pools, and coastal water (Brausch and Rand, 2011;Mao et al., 2019). For example, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), one of the most popular BP-type UV filters, was reported to occur in Songhua river in China at a concentration ranging from 2.3 to 122 ng L − 1 (Zhang et al., 2011a(Zhang et al., , 2011b, and in an outdoor swimming pool of South Bohemia, at a concentration around 620 ng L − 1 (Grabicova et al., 2013). ...
Benzophenone(BP)-type UV filters are continuously released into various aquatic environments via the effluent discharge of wastewater treatment plants (WWTPs) and recreational activities in coastal beaches. In this study, we developed a robust and reliable sampling approach, diffusive gradients in thin-films (DGT), for seasonal monitoring of six BP derivatives in coastal waters to investigate their occurrence and environmental risk. The binding capacities of both XAD-2 and HLB gels for test BPs were over 252 μg with no significant deterioration in marine environment, suggesting that theoretically, DGT is capable of sampling for at least 3 months effectively. The diffusion coefficients of BPs for freshwater and seawater were determined for the first time. The sampling performance showed no dependence on environmental conditions including pH (4.0–8.5), ionic strength (0.0001–0.5 M) and dissolved organic matter (0–20 mg L⁻¹). The developed DGT samplers were successfully applied in a river estuary linked to a WWTP and a bathing beach at different periods of one year. Results showed that the concentrations of BPs in the coastal waters were dependent on seasonal variation. The highest level in summer and the ecological risk should be considered based on the risk quotient values. These results demonstrated that the present DGT method is suitable for measuring, characterization, and risk assessment of BPs in freshwater and marine environment.
... Furthermore, our study intends to discuss the two top-priority pollutants revealed by meta-analysis: 4-methylbenzylidenecamphor (4-MBC) and benzophenone-3 (BP-3), focusing on their presence in marine ecosystems and adverse ecotoxicological effects on marine invertebrates. The marine environment was selected over freshwater as there were fewer available investigations in the marine environment (Arpin-Pont et al. 2016;Brausch and Rand 2011;Cadena-Aizaga et al. 2020;Mao et al. 2019). Moreover, marine invertebrates were chosen as invertebrates encompass more than 95% of the animal kingdom species, most belonging to aquatic ecosystems, and because marine invertebrates are at intermediate levels of the food chain, representing species of ecological relevance in the biodiversity of ecosystems (Deidda et al. 2021;Mather 2013). ...
The potential adverse effects of UV-filter pollution in marine environments have been the focus of research in recent years. This systematic review aims to determine the extent of this emerging problem, both quantitatively and qualitatively, combining temporal and science mapping analyses to explore the development of the field of UV-filters in the marine environment (from 1990 to 2021), and to outline new research frontiers. The temporal trend analysis revealed an exponential growth of published studies over the last decade (70% since 2016), confirming the emerging role of this topic in environmental science. The meta-analysis determined that 4-methylbenzylidene-camphor (4-MBC) and benzophenone-3 (BP-3) are top-priority environmental pollutants due to their increasing usage and, in turn, a frequent occurrence in marine ecosystems. This meta-analysis determined the focus on these two contaminants for this review. A critical discussion of the applications, regulatory aspects, and environmental occurrences of these selected compounds was provided. The present study also focused on the most recent (2015–2021) field and laboratory studies investigating the ecotoxicological impacts of 4-MBC and BP-3 on marine invertebrates. This review highlights the need for more research efforts to fill the knowledge gaps on the realistic effects these compounds may have when considered individually, in combination, or as subsequent exposures. Overall, this review aims to establish guidelines for further studies to understand the effect of UV-filters on marine ecosystems and marine invertebrate communities.
... Benzophenone-3 (oxybenzone, BP3) and 2-ethylhexyl 4-methoxycinnamate (octinoxate, EHMC) are the two most commonly used UVFs ☆ This paper has been recommended for acceptance by Eddy Y. Zeng. in sunscreens worldwide (Glanz et al., 2022), and they have been extensively detected in wastewater (e.g. BP3 average concentrations of 12,000 ng/L) (Mao et al., 2019) and environmental matrices (Agawin et al., 2022;Cadena-Aizaga et al., 2022;Wang et al., 2022). For example, BP3 highest concentration found was 1037 ng/g dw in cod livers, and EHMC was frequently detected with even higher concentrations in bivalves, fish and crustaceans (Huang et al., 2021). ...
UV filters (UVFs) and paraben preservatives (PBs) are widely used components in many personal care products. However, there has been a rising concern for their endocrine-disrupting effects on wildlife once they reach aquatic ecosystems via recreative activities and wastewater treatment plants effluents. This study addresses UVFs and PBs occurrence in seawater and sediment impacted by tourism and sewage discharges along the coast of Mahdia, center East Tunisia. Samples of water and sediment were collected for 6 months from 3 coastal areas. Among the 14 investigated UVFs, 8 were detected in seawater and 4 were found in sediment. All PBs were present in seawater and only methylparaben (MePB) was detected in sediment. Benzophenone-3 (oxybenzone, BP3), benzocaine (EtPABA), and MePB were present in all water samples with concentrations in the ranges 16.4–66.9, 7.3–37.7, and 17.6–222 ng/L, respectively. However, the highest value, 1420 ng/L, corresponded to octinoxate (EHMC). In sediments, avobenzone (AVO), 4-methyl benzylidene camphor (4MBC), EHMC, 5-methyl-1-H-benzotriazole (MeBZT), and MePB were detected at concentrations within the range 1.1–17.6 ng/g dw, being MePB the most frequently detected (89%). MePB and MBZT presented the highest sediment-water partition coefficients and MePB also showed a positive correlation with total suspended solids’ water content. Overall, pollutants concentrations remained rather constant along the sampling period, showing little seasonal variation. This study constitutes the first monitoring of UVFs and PBs on the Tunisian coastline and provides occurrence data for reference in further surveys in the country.
... UV stabilisers, including benzotriazole UV stabilisers (BZT-UVs), have been reported in Arctic and non-Arctic biota [34,35]. These chemicals have attracted increasing scientific and public concern because of their large production volumes, occurrence in the environment, and potential environmental risks [34,36]. Some BZT-UVs have been identified for risk management action under the Canadian federal Chemicals Management Plan [37], listed in the High Production Volume Challenge Program and Toxic Substances Control Act Inventory by the United States or classified as Substances of Very High Concern in Europe [38]. ...
Through ingestion and subsequent egestion, Arctic seabirds can bioaccumulate microplastics at and around their colony breeding sites. While microplastics in Arctic seabirds have been well documented, it is not yet understood to what extent these particles can act as transport vehicles for plastic-associated contaminants, including legacy persistent organic pollutants (POPs), trace metals, and organic additives. We investigated the occurrence and pattern of organic and inorganic contaminants and the co-contaminants of microplastics in two seabird species from the Canadian Arctic — northern fulmar (Fulmarus glacialis) and black-legged kittiwake (Rissa tridactyla). We found that fulmars had higher levels of plastic contamination and emerging organic compounds (known to be plastic additives) than kittiwakes, whereas higher concentrations of legacy POPs were found in kittiwakes than the fulmars. Furthermore, fulmars, the species with the much larger foraging range (∼200 km), had higher plastic pollution and overall contaminant burdens, indicating that birds may be acting as long-range transport vectors for plastic-associated pollution. Our results suggest a potential connection between plastic additive contamination and plastic pollution burdens in the bird stomachs, highlighting the importance of treating plastic particles and plastic-associated organic additives as co-contaminants rather than separate pollution issues.
... Plastic additives can leach from MPs into aquatic environments or within organisms (Jang et al., 2016;Hahladakis et al., 2018) and may aggravate the adverse effects of MPs on aquatic biota (Luo et al., 2019;Zimmermann et al., 2020). Among plastic additives, benzophenone-3 (BP-3, an ultraviolet stabilizer) is of concern given its high persistence and bioaccumulation in aquatic environments (Mao et al., 2019). BP-3 has been detected in the effluents of wastewater treatment plants (Kasprzyk-Hordern et al., 2009;Liu et al., 2012), rivers (Kameda et al., 2011;Li et al., 2014b), and lakes (Poiger et al., 2004;Balmer et al., 2005). ...
Maternal exposure to microplastics (MPs) plays an important role in the fitness of unexposed progeny. In this study, the transgenerational effects of polyethylene MP fragments (17.35 ± 5.50 µm) containing benzophenone‐3 (BP-3; 2.85 ± 0.16% w/w) on chronic toxicity (21 d) in Daphnia magna were investigated across four generations. Only D. magna in the F0 generation was exposed to MP fragments, MP/BP-3 fragments, and BP-3 leachate to identify the transgenerational effect in the F3 generation. The mortality of D. magna induced by MP and MP/BP-3 fragments was recovered in the F3 generation, but somatic growth and reproduction significantly decreased compared to the control. Additionally, reproduction of D. magna exposed to BP-3 leachate significantly decreased in the F3 generation. These findings confirmed the transgenerational effects of MP fragment and BP-3 additive on D. magna. Particularly, the adverse effect on D. magna reproduction seemed to be cumulative across four generations for MP/BP-3 fragments, while it was an acclimation trend for BP-3 leachate. However, there was no significant difference in global DNA methylation in D. magna across four generations, thus requiring a gene-specific DNA methylation study to identify different epigenetic transgenerational inheritance.
The analysis of UV filters (UVFs) in water has become increasingly important due to their adverse effects on aquatic organisms and humans. This study describes a method for the determination of benzophenone derivatives UVF in wastewater samples. The selected UVFs are 2‐hydroxy‐4‐methoxybenzophenone (BP‐3), 2,4‐dihydroxybenzophenone (BP‐1), 4‐hydroxybenzophenone (4HB), 2,2′‐dihydroxy‐4‐methoxybenzophenone (DHMB) and lastly, 4,4′‐dihydroxybenzophenone (4DHB). The method includes solid‐phase extraction (SPE) of analytes from wastewater followed by on‐line derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA) and analysis with GC‐MS/MS. Method validation studies resulted in good recoveries (86–112%), relative standard deviation RSD = 0.8 and 7.3%, the limits of detection LODs = 1.00–10.8 ng/L, and the limits of quantification LOQs = 3.00–32.3 ng/L. The method was successfully applied to domestic wastewater samples collected from influent and effluent of touristic hotels’ biological wastewater treatment plants. BP‐3 (24–1765 ng/L), BP‐1 (8–703 ng/L), 4HB (26–96 ng/L), and 4DHB (20–22 ng/L) were the common benzophenone derivatives in the influent wastewater while effluent contained mainly BP‐1 (8–32 ng/L), 4HB (12–57 ng/L) and 4DHB (20–102 ng/L). These results indicate that BP‐3 and BP‐1 are biodegraded in the treatment processes. However, 4HB and 4DHB are resistant to degradation and they are the main benzophenone metabolites discharged to receiving media.
Benzophenones (BPs) are substances used in the production of sunscreens, cosmetics, and personal care products. However, there is a lack of knowledge of BPs in wild animals. Therefore, the study aimed to assess the concentration of selected BPs commonly used in the cosmetic industry in guano samples collected from 4 colonies of greater mouse-eared bats ( Myotis myotis ). Liquid chromatography with tandem mass spectrometry (LC-MS/MS) was used to determine guano concentrations of benzophenone 1 (BP-1), benzophenone 2 (BP-2), benzophenone 3 (BP-3) and benzophenone 8 (BP-8). BP-1 levels above the method quantification limit (MQL) were noted in 97.5% of samples and fluctuated from <0.1 ng/g to 259 ng/g (mean 41.50 ng/g, median 34.8). The second most common was BP-3, which fluctuated from <0.1 ng/g to 19 ng/g (mean 6.67 ng/g, median 5.05), and its levels higher than MQL were observed in 40% of samples. BP-2 and BP-8 concentrations did not exceed the method detection limit (0.04 ng/g) in any analyzed sample. There were visible differences in the BP-1 and BP-3 levels among the studied bat colonies. Mean BP-1 concentration fluctuated from 11.23±13.13 ng/g to 76.71±65.51 ng/g and differed significantly between the colonies. Mean BP-3 concentration fluctuated from 5.03±6.03 ng/g to 9.18±7.65 mg/g, but it did not differ significantly between the colonies. The results show that guano is a suitable matrix for the assessment of wildlife exposure to BPs. This could be particularly advantageous in protected species, where not disturbing and stressing the animals are crucial.
Based on derivatization of commercial poly(ethylene‐co‐vinyl acetate) (EVA), novel macromolecular UV‐absorbers with polyethylene (PE) backbones and ferrocene side groups are presented in this study. The structures and properties of the polymers were analyzed using various techniques including Fourier transform infrared spectroscopy (FT‐IR), proton nuclear magnetic resonance (¹H NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscope (SEM), and UV visible absorption spectroscopy. UV analysis experiments have shown that PE‐grafted ferrocenyl ester (PE‐g‐FE) and PE‐grafted azacyclo‐ferrocene (PE‐g‐AF) with ferrocene side groups have the potential to act as UV absorbers. By using the polymers as additives for commercial PE, the anti‐migration experiment demonstrates that PE‐g‐AF, with a heterocyclic structure, exhibits superior anti‐migration performance than the ester‐linked PE‐g‐FE. Furthermore, in comparison to commercial small‐molecular UV absorbers (UV‐329), the PE‐g‐AF absorber not only exhibits better UV absorption performance but also demonstrates almost zero migration behavior within the PE matrix.
Ultraviolet (UV) filters are emerging contaminants that have been found in high concentrations in human tissues. Food intake is generally considered to be the primary route of human exposure to contaminants. In this study, 184 composite food samples, prepared from 4268 individual samples in eight categories collected from 23 Chinese provinces for the sixth Chinese total diet study, were analyzed. The total and median UV filter concentrations in food samples were 1.5-68.3 and 7.9 ng/g wet weight, respectively. The highest median concentrations were found in decreasing order in meat, cereals, and legumes. In total, 15 UV filters were analyzed. 2-Ethylhexyl salicylate, homosalate, and 2-ethylhexyl-4-methoxycinnamate were dominant and made median contributions of 34.1%, 22.6%, and 14.5%, respectively, and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol contributed the median of 0.03%, of the total UV filter concentrations. The estimated total daily UV filter intake in animal-origin foods and total UV filter concentration in human milk from the same province were significantly correlated (r = 0.44, p < 0.05). Predicted absorption, distribution, metabolism, and elimination properties led to 10 UV filters being prioritized as most likely to be retained in human tissues. The prioritization results and toxicity assessments indicated that octocrylene and 2-ethylhexyl-4-methoxycinnamate have stronger effects in vivo and therefore require more attention than others.
Radical-coupled transformation products (TPs) have been identified as the byproducts of various transformation processes, including both natural attenuation and artificial treatments, of phenolic micropollutants. Benzophenone-3 (BP-3), an organic UV filter of emerging concern, has been previously reported with ubiquitous occurrence in the natural environment and water bodies. Current research has demonstrated how TPs are formed from BP-3 when it is treated with manganese oxide (MnO2). The ecological and toxicological risks of these TPs have also been assessed. Polymerization of BP-3 through radical coupling was observed as the major pathway by which BP-3 is transformed when treated with MnO2. These radical-coupled TPs haven't shown further degradation after formation, suggesting their potential persistence once occurred in the environment. In silico experiments predict the radical-coupled TPs will increase in mobility, persistence and ecotoxicity. If true, they also represent an ever-increasing threat to the environment, ecosystems and, most immediately, aquatic living organisms. In addition, radical-coupled TPs produced by MnO2 transformation of BP-3 have shown escalated estrogenic activity compared to the parent compound. This suggests that radical coupling amplifies the toxicological impacts of parent compound. These results provide strong evidence that radical-coupled TPs with larger molecular sizes are having potential adverse impacts on the ecosystem and biota.
Fungi have protruded with enormous development in the repository of drug discovery, making them some of the most attractive sources for the synthesis of bio-significant and structural novel metabolites. Benzophenones are structurally unique metabolites with phenol/carbonyl/phenol frameworks, that are separated from microbial and plant sources. They have drawn considerable interest from researchers due to their versatile building blocks and diversified bio-activities. The current work aimed to highlight the reported data on fungal benzophenones, including their structures, occurrence, and bioactivities in the period from 1963 to April 2023. Overall, 147 benzophenones derived from fungal source were listed in this work. Structure activity relationships of the benzophenones derivatives have been discussed. Also, in this review, a brief insight into their biosynthetic routes was presented. This work could shed light on the future research of benzophenones.
Benzophenone-n compounds (BPs) are applied in a broad spectrum of commercial products, one of which is sunscreen. These chemicals are frequently detected in a variety of environmental matrices worldwide, especially water bodies. BPs are defined as emerging contaminants as well as endocrine-disrupting contaminants; thus, it has become necessary to develop aggressive and green treatments to remove BPs. In this study, we used immobilised BP-biodegrading bacteria linked to reusable magnetic alginate beads (MABs). The MABs were added to a sequencing batch reactor (SBR) system to enhance the removal of 2,4-dihydroxybenzophenone (BP-1) and oxybenzone (BP-3) from sewage. The BP-1 and BP-3 biodegrading bacteria in the MABs consisted of strains from up to three genera to allow for efficient biodegradation. The strains used were Pseudomonas spp., Gordonia sp., and Rhodococcus sp. The optimal composition of the MABs consisted of 3% (w/v) alginate and 10% (w/v) magnetite. The MABs resulted in 60.8%-81.7% recovery by weight after 28 days, and there was a continuous release of bacteria. Moreover, the biological treatment of the BPs sewage improved after adding 100 g of BP1-MABs (1:27) and also 100 g BP3-MABs (1:27) into the SBR system at a hydraulic retention time (HRT) of 8 h. Compared with the SBR system without MABs, the removal rates of BP-1 and BP-3 increased from 64.2% to 71.5% and from 78.1% to 84.1%, respectively. Furthermore, the COD removal increased from 36.1% to 42.1%, and total nitrogen increased from 30.5% to 33.2%. Total phosphorus remained constant at 29%. The bacterial community analysis showed that the Pseudomonas population was <2% before the MAB addition, but increased to 56.1% by day 14. In contrast, the Gordonia sp. And Rhodococcus sp. Populations (<2%) remained unchanged throughout the 14-day treatment period.
To carry out risk assessments of benzophenone-type UV filters (BPs), fast and accurate analytical methods are crucial to determine and monitor levels in the environment. This study presents an LC-MS/MS method that requires minimal sample preparation and yet can identify 10 different BPs in environmental samples such as surface or wastewater resulting in a LOQ range from 2 to 1060 ng/L. The method suitability was tested through environmental monitoring, which showed that, BP-4 is the most abundant derivative found in the surface waters of Germany, India, South Africa and Vietnam. BP-4 levels correlate with the WWTP effluent fraction of the respective river for selected samples in Germany. Peak values of 171 ng/L for 4-hydroxybenzophenone (4-OH-BP), as measured in Vietnamese surface water, already exceed the PNEC value of 80 ng/L, elevating 4-OH-BP to the status of a new pollutant that needs more frequent monitoring. Moreover, this study reveals that during biodegradation of benzophenone in river water, the transformation product 4-OH-BP is formed which contain structural alerts for estrogenic activity. By using yeast-based reporter gene assays, this study provides bio-equivalents of 9 BPs, 4-OH-BP, 2,3,4-tri-OH-BP, 4-cresol and benzoate and complements the existing structure-activities relationships of BPs and their degradation products.
Background: Plastics have conveyed great benefits to humanity and made possible some of the most significant advances of modern civilization in fields as diverse as medicine, electronics, aerospace, construction, food packaging, and sports. It is now clear, however, that plastics are also responsible for significant harms to human health, the economy, and the earth’s environment. These harms occur at every stage of the plastic life cycle, from extraction of the coal, oil, and gas that are its main feedstocks through to ultimate disposal into the environment. The extent of these harms not been systematically assessed, their magnitude not fully quantified, and their economic costs not comprehensively counted.
Goals: The goals of this Minderoo-Monaco Commission on Plastics and Human Health are to comprehensively examine plastics’ impacts across their life cycle on: (1) human health and well-being; (2) the global environment, especially the ocean; (3) the economy; and (4) vulnerable populations—the poor, minorities, and the world’s children. On the basis of this examination, the Commission offers science-based recommendations designed to support development of a Global Plastics Treaty, protect human health, and save lives.
Conclusions: It is now clear that current patterns of plastic production, use, and disposal are not sustainable and are responsible for significant harms to human health, the environment, and the economy as well as for deep societal injustices.
The main driver of these worsening harms is an almost exponential and still accelerating increase in global plastic production. Plastics’ harms are further magnified by low rates of recovery and recycling and by the long persistence of plastic waste in the environment. The thousands of chemicals in plastics—monomers, additives, processing agents, and non-intentionally added substances—include amongst their number known human carcinogens, endocrine disruptors, neurotoxicants, and persistent organic pollutants. These chemicals are responsible for many of plastics’ known harms to human and planetary health. The chemicals leach out of plastics, enter the environment, cause pollution, and result in human exposure and disease. All efforts to reduce plastics’ hazards must address the hazards of plastic-associated chemicals.
Benzophenone-type UV filters (BPs) are ubiquitous contaminants in aquatic environments, possibly posing ecological risks to aquatic populations. So far, little is known about the potential adverse effects of BPs on amphibians. Given their potential estrogenic property, we investigated the detrimental effects of the commonly used BPs, BP-3, BP-2, and BP-1, on testis development in amphibians using Xenopus laevis as a model species. Following exposure to 10, 100, 1000 nM BP-3, BP-2, or BP-1 from stages 45/46 to 52, tadpoles presented morphological abnormal testes, characterized by reduced gonomere size and testis area, coupled with suppressed cell proliferation. Meanwhile, the downregulation of testis-biased gene expression and the upregulation of ovary-biased gene expression were observed in BPs-treated testes. Moreover, the estrogen receptor (ER) antagonist ICI 182780 significantly antagonized ovary-biased gene upregulation caused by BPs, suggesting that the effects of BPs on testis differentiation could be mediated by ER, at least partially. Of note, the effects of BPs were not concentration-dependent, but the lowest concentration generally exerted significant effects. Altogether, these observations indicate that the three BPs inhibited testis differentiation and exerted feminizing effects. Importantly, when BP-2 exposure was extended to two months post-metamorphosis, testes of froglets were generally less-developed, with relatively fewer spermatocytes, more spermatogonia, and poorly formed seminiferous tubules. Considering the fact that the lowest concentration (10 nM) of BPs in this study are detectable in aquatic environments, we conclude that BP-3, BP-2, and BP-1, even at environmentally relevant concentrations, can retard testis differentiation at pre-metamorphic stages and cause testis dysgenesis after metamorphosis in the amphibian X. laevis. Our findings suggest that ubiquitous BPs in aquatic environments could pose a potential risk to amphibians.
Benzophenone-3 (BP-3) often used as a UV filter in various products and an endocrine disruptor. In this work, we exposed the clown anemonefish to 10 μg/L and 50 μg/L BP-3 for 7 and 14 days. Liver histological, biochemical analysis, and transcriptome sequencing were used to explore the mechanism of the lipid metabolism disorder in the liver of three-month-old clown anemonefish treated with BP-3. The histological and biochemical analysis showed that BP-3 induces morphological changes and lipid droplet accumulation, and the lipid content, lipase, and antioxidant enzyme activity were abnormal. After treatment with 10 μg/L and 50 μg/L BP-3 for 7 days, the transcriptome analysis further demonstrated that the KEGG analysis revealed that the differentially expressed genes (DEGs) were mainly associated with fat digestion and absorption, PPAR signaling pathway, circadian rhythm, and mineral absorption pathways; After 10 μg/L and 50 μg/L of BP-3 exposure for 14 days, the KEGG analysis were mainly associated with circadian rhythm, circadian rhythm-fly, protein processing in the endoplasmic reticulum, and beta-alanine metabolism pathways. Several key genes were involved in the process of liver lipid metabolism, including CD36, APoA-Ⅰ, FABP, LPL, ACS, and PEPCK. The qRT-PCR validation results showed that eight genes (CYP8B1, FABP1, LPL, MGAT, PEPCK, PER1, PSMB4, PSME2) were significantly down-regulated, and the other two genes (Fbxl3, RXR) were significantly up-regulated after 7 days of BP-3 exposure. Similarly, eleven genes (AMPK, ARNTL, Bmal1, CASP3, CYC, CYP2J, CYP2U1, GSK3A, PEPCK, RAC1, RORA) were significantly up-regulated, and the other four genes (NR1D1, PER1, PTGDS, HLF) were significantly down-regulated after 14 days of BP-3 exposure. In conclusion, our results elucidate the physiological and molecular responses to BP-3 exposure in the liver lipid metabolism of clown anemonefish, and these findings reveal that the regulation of lipid metabolism is disturbed when clown anemonefish is exposed to UV filters.
Benzophenone-n (BPs) is an emerging endocrine-disrupting contaminant that can be applied to different commercial products including UV-filters. BPs are toxic to microorganisms, coral, and animals. This study aims to demonstrate the use of laboratory-scale SBR to remove 2,4-dihydroxybenzophenone (BP-1) and oxybenzophenone (BP-3) and to investigate extracellular polymeric substance (EPS) production and functions under different hydraulic retention time (HRT) and operating stages. HRT period focused on removal of BPs and different stages focused on EPS content. The results show that the removal of BPs is high when HRT is increased from 8 (68.9% for BP-1/78.5% for BP-3) to 48 h (96.8%/98.0%, respectively); and favoured in reaction stage (aerobic condition) (80.33%/90.23%, respectively). In the view of EPS, protein (EPS-PN) content increases from 57.8 μg/L to 119.8 μg/L when HRT is increased from 8 to 48 h; however, polysaccharides (EPS-PS) show no relationship with HRT. In different stages, both EPS content reach the maximum (132.2 μg/L and 194.2 mg/L, respectively) during idle stage, and fluctuate in first 3 h of reaction stage and later recover to 117.1 μg/L and 160.6 mg/L, respectively. The next-generation sequencing (NGS) results show that different HRTs promote different dominant strains, but both communities are similar at different stages.
Organic ultraviolet filters, including 4-hydroxybenzophenone (4-HBP) and 2,4-dihydroxybenzophenone (BP-1), are persistent emerging contaminants whose presence in the environment has been a threat to aquatic organisms due to their endocrine disruptor’s properties. Their efficient removal from the environment became a priority for the scientific community, especially for finding suitable decontamination technological processes. Up to now, there are no studies reporting the biodegradation of 4-hydroxybenzophenone and 2,4-dihydroxybenzophenone by a specific bacterial strain. In this paper, there were tested, in-vitro, the 4-hydroxybenzophenone and 2,4-dihydroxybenzophenone biodegradation potential of two Gram-positive (Staphylococcus aureus and Enterococcus faecalis) and two Gram-negative (Salmonella typhimurium and Serratia rubidae), as biological models. The 2,4-dihydroxybenzophenone biodegradation rate, after 24 h incubation with bacterial strains, was 26.7% induced by Staphylococcus aureus and 14.7% by Salmonella thiphymurium. The 4-hydroxybenzophenone biodegradation process was a more specific one since only Gram-negative bacterial strains were successful in biodegrading it. The 4-hydroxybenzophenone biodegradation rates reached up to 12.7% after 24 h of incubation in presence of Salmonella thyphimurium and up to 24.0% after 24 h of incubation with Serratia rubidae. The 4-HBP biodegradation process induced by Serratia rubidae was limited to generation of benzophenone and a multi-hydroxylated derivative of 4-HBP by-products. The data obtained in this study gave important information regarding the 4-hydroxybenzophenone and 2,4-dihydroxybenzophenone potential biodegradation pathways by single bacterial strains.
Benzophenone-3 (BP-3) is an emerging environmental pollutant used in personal care products, helping to reduce the risk of ultraviolet radiation to human skin. The BP-3 removal potential from soil by tobacco (Nicotiana tabacum) assisted with Methylophilus sp. FP-6 was explored in our previous study. However, the reduced BP-3 remediation efficiency by FP-6 in soil and the inhibited plant growth by BP-3 limited the application of this phytoremediation strategy. The aim of the present study was to reveal the potential roles of betaine, as the methyl donor of methylotrophic bacteria and plant regulator, in improving the strain FP-6-assisted phytoremediation capacity of BP-3 contaminated soil. The results revealed that strain FP-6 could use betaine as a co-metabolism substrate to enhance the BP-3 degradation activity. About 97.32% BP-3 in soil was effectively removed in the phytoremediation system using tobacco in combination with FP-6 and betaine for 40 d while the concentration of BP-3 in tobacco significantly reduced. Moreover, the biomass and photosynthetic efficiency of plants were remarkably improved through the combined treatment of betaine and strain FP-6. Simultaneously, inoculation of FP-6 in the presence of betaine stimulated the change of local microbial community structure, which might correlate with the production of a series of hydrolases and reductases involved in soil carbon, nitrogen and phosphorus cycling processes. Meantime, some of the dominant bacteria could secrete various multiple enzymes involved in degrading organic pollutants, such as laccase, to accelerate the demethylation and hydroxylation of BP-3. Overall, the results from this study proposed that the co-metabolic role of betaine could be utilized to strengthen microbial-assisted phytoremediation process by increasing the degradation ability of methylotrophic bacteria and enhancing plant tolerance to BP-3. The present results provide novel insights and perspectives for broadening the engineering application scope of microbial-assisted phytoremediation of organic pollutants without sacrificing economic crop safety.
To avoid the harmful effects of UV radiation, benzophenone-type UV filters (BPs) are widely used in personal care products and other synthetic products. Biomonitoring studies have shown the presence of BPs in various human biological samples, raising health concerns. However, there is a paucity of data on the global human exposure to this group of contaminants. In this study, we compiled data on the body burden of BPs along with the possible exposure routes and biotransformation pathways. BPs can easily penetrate the skin barrier and thus, they can be absorbed through the skin. In the human body, BPs can undergo Phase I (mainly demethylation and hydroxylation) and Phase II (mainly glucuronidation and sulfation) biotransformations. From a total of 158 studies, most of the studies are related to urine (concentration up to 92.7 mg L–1), followed by those reported in blood (up to 0.9 mg L–1) and milk (up to 0.8 mg L–1). Among BPs, benzophenone-1 and benzophenone-3 are the most commonly detected congeners. The body burden of BPs is associated with various factors, including the country of residence, lifestyle, income, education level, and ethnicity. The presence of BPs in maternal urine (up to 1.1 mg L–1), placenta (up to 9.8 ng g–1), and amniotic fluid (up to 15.7 μg L–1) suggests potential risks of prenatal exposure. In addition, transplacental transfer of BPs is possible, as demonstrated by their presence in maternal serum and cord serum. The possible association of BPs exposure and health effects was discussed. Future human biomonitoring studies and studies on the potential health effects are warranted. Overall, this review provides a summary of the global human exposure to BPs and can serve as supporting evidence to guide usage in order to protect humans from being exposed to BPs.
The presence of personal care products (PCPs) in the marine environment is of major concern. PCPs, UV filters, and musks can enter the marine environment indirectly through wastewater or directly via recreational activities. We conducted this study to document patterns in the occurrence of seven PCPs at three coastal sites impacted by recreational activities during 1 day. The study focused on diurnal variations in these seven PCPs in seawater and indigenous mussels. In seawater, UV filters showed diurnal variations that mirrored variations in recreational activities at the sites. Ethylhexyl methoxycinnamate (EHMC) and octocrylene (OC) water concentrations increased from under the limit of quantification in the morning to 106 and 369 ng/L, respectively, when recreational activities were the highest. In mussels, diurnal variations in OC were observed, with the lowest concentrations recorded in the morning and then increasing throughout the day. As Mytilus spp. are widely used as sentinels in coastal pollution monitoring programs (mussel watch), our findings on diurnal variations could enhance sampling recommendations for recreational sites impacted by PCPs.
Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g(-1) dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.
Magnetic solid-phase extraction is one of the most promising new extraction methods for liquid samples before ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. Several types of materials, including carbonaceous ones, have been prepared for this purpose. In this paper, for the first time, the preparation, characterization, and sorption capability of Fe3O4-graphitized carbon black (mGCB) composite toward some compounds of environmental interest were investigated. The synthesized mGCB consisted of micrometric GCB particles with 55 m(2) g(-1) surface area bearing some carbonyl and hydroxyl functionalities and the surface partially decorated by Fe3O4 microparticles. The prepared mGCB was firstly tested as an adsorbent for the extraction from surface water of 50 pollutants, including estrogens, perfluoroalkyl compounds, UV filters, and quinolones. The material showed good affinity to many of the tested compounds, except carboxylates and glucoronates; however, some compounds were difficult to desorb. Ten UV filters belonging to the chemical classes of benzophenones and p-aminobenzoates were selected, and parameters were optimized for the extraction of these compounds from surface water before UHPLC-MS/MS determination. Then, the method was validated in terms of linearity, trueness, intra-laboratory precision, and detection and quantification limits. In summary, the method performance (trueness, expressed as analytical recovery, 85-114%; RSD 5-15%) appears suitable for the determination of the selected compounds at the level of 10-100 ng L(-1), with detection limits in the range of 1-5 ng L(-1). Finally, the new method was compared with a published one, based on conventional solid-phase extraction with GCB, showing similar performance in real sample analysis. Graphical Abstract Workflow of the analytical method based on magnetic solid-phase extraction followed by LC-MS/MS determination.
In this work, the presence of selected emerging contaminants has been investigated in two reservoirs, La Fe (LF) and Rio Grande (RG), which supply water to two drinking water treatment plants (DWTPs) of Medellin, one of the most populated cities of Colombia. An analytical method based on solid-phase extraction (SPE) of the sample followed by measurement by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) was developed and validated for this purpose. Five monitoring campaigns were performed in each reservoir, collecting samples from 7 sites (LF) and 10 sites (RG) at 3 different depths of the water column. In addition, water samples entering in the DWTPs and treated water samples from these plans were also analysed for the selected compounds. Data from this work showed that parabens, UV filters and the pharmaceutical ibuprofen were commonly present in most of the reservoir samples. Thus, methyl paraben was detected in around 90% of the samples collected, while ibuprofen was found in around 60% of the samples. Water samples feeding the DWTPs also contained these two compounds, as well as benzophenone at low concentrations, which was in general agreement with the results from the reservoir samples. After treatment in the DWTPs, these three compounds were still present in the samples although at low concentrations (<40 ng/L), which evidenced that they were not completely removed after the conventional treatment applied. The potential effects of the presence of these compounds at the ppt levels in drinking water are still unknown. Further research is needed to evaluate the effect of chronic exposure to these compounds via consumption of drinking water.
Considering combinatorial optimality of functional group analysis, speciation, solution chemistry complexity, Pd(II) adsorption–desorption characteristics, this article addresses the competence and efficacy of anion exchange resins namely Amberlite IRA958, Dowex Marathon MSA, Lewatit TP214, and Amberlyst A21 commercial resins. Based on preliminary batch adsorption experiments conducted in the range of 2−10 pH, 0.2−2 g L⁻¹ adsorbent dosage, and 5−1080-min contact time, the optimal adsorption process parameters refer to 4 pH, 1.6, and 1.4 g L⁻¹ adsorbent dosage, and 840- and 720-min contact time for Amberlite IRA958 and Dowex Marathon MSA resins, respectively. Among alternate models, the best-fit models refer to the Freundlich isotherm and pseudo-second-order kinetic models to represent Pd(II) adsorption data obtained for both Dowex Marathon MSA and Amberlite IRA958 resins. Based on the Langmuir isotherm, the maximum monolayer adsorption capacity was evaluated to be 185.16 and 166.67 mg g⁻¹ for Dowex Marathon MSA and Amberlite IRA958 resins, respectively. For model electroless plating solutions as adsorbate system possessing desired solution chemistry complexity and resin cost, nitrogen- and oxygen-containing Amberlyst A21 resin is concluded to be optimal resin. This is not in agreement with the generalized rule of thumb that considers sulfur–nitrogen functional group containing commercial resins to be effective than resins with nitrogen–oxygen functional groups. Due to functional group interactions with the noble metal, no other by-products or exchanged chemicals have been produced in due course of Pd(II) adsorption process, which can be also regarded as an added advantage of the process.
Graphical abstract
Benzophenone-3 (BP-3; oxybenzone) is an ingredient in sunscreen lotions and personal-care products that protects against the damaging effects of ultraviolet light. Oxybenzone is an emerging contaminant of concern in marine environments-produced by swimmers and municipal, residential, and boat/ship wastewater discharges. We examined the effects of oxybenzone on the larval form (planula) of the coral Stylophora pistillata, as well as its toxicity in vitro to coral cells from this and six other coral species. Oxybenzone is a photo-toxicant; adverse effects are exacerbated in the light. Whether in darkness or light, oxybenzone transformed planulae from a motile state to a deformed, sessile condition. Planulae exhibited an increasing rate of coral bleaching in response to increasing concentrations of oxybenzone. Oxybenzone is a genotoxicant to corals, exhibiting a positive relationship between DNA-AP lesions and increasing oxybenzone concentrations. Oxybenzone is a skeletal endocrine disruptor; it induced ossification of the planula, encasing the entire planula in its own skeleton. The LC50 of planulae exposed to oxybenzone in the light for an 8- and 24-h exposure was 3.1 mg/L and 139 µg/L, respectively. The LC50s for oxybenzone in darkness for the same time points were 16.8 mg/L and 779 µg/L. Deformity EC20 levels (24 h) of planulae exposed to oxybenzone were 6.5 µg/L in the light and 10 µg/L in darkness. Coral cell LC50s (4 h, in the light) for 7 different coral species ranges from 8 to 340 µg/L, whereas LC20s (4 h, in the light) for the same species ranges from 0.062 to 8 µg/L. Coral reef contamination of oxybenzone in the U.S. Virgin Islands ranged from 75 µg/L to 1.4 mg/L, whereas Hawaiian sites were contaminated between 0.8 and 19.2 µg/L. Oxybenzone poses a hazard to coral reef conservation and threatens the resiliency of coral reefs to climate change.
A new nitrogen-containing carbon nanoparticles (N-CNPs) coated fiber was developed for solid phase microextraction (SPME) with direct electrodeposition of polyaniline coating on etched stainless steel wire using potentiostatic technique followed by carbonization at 500 oC under nitrogen atmosphere. The extraction performance of N-CNPs coating was investigated towards polycyclic aromatic hydrocarbons (PAHs), ultraviolet (UV) filters and phthalate acid esters (PAEs) in water samples coupled to high performance liquid chromatography with UV detection (HPLC-UV). This N-CNPs coating shows excellent selectivity for UV filters compared to that for PAHs and PAEs. Under optimized conditions, the linearity of UV filters was in the range 0.02-200 g•L-1 with corresponding correlation coefficient of 0.9921-0.9993. The recoveries ranged from 89.2% to 119%. The relative standard deviations of single fiber were between 4.83% and 7.82% (n=5) and fiber-to-fiber were between 7.94% and 10.14% (S/N = 3). Their limits of detection and the limits of quantitation ranged from 0.06-0.2 g•L-1 and 0.02-0.67 g•L-1, respectively. The proposed SPME-HPLC-UV procedure was successfully used for selective concentration and sensitive determination of UV filters in environment water samples. Furthermore this new robust fiber was easily prepared in reproducible manner.
The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/gdryweight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7ng/gd.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23ng/gd.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04-0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web.
Copyright © 2015. Published by Elsevier B.V.
Isatin and 1H-1,2,3-triazoles are two classes of compounds with great prominence in organic synthesis and medicinal chemistry as they are heterocycle nuclei with a high reactivity allowing to obtain several compounds with important biological properties. Herein, the synthesis of novel 5'-(4-alquil/aril-1H-1,2,3-triazole)-isatin via reaction of 1,3-dipolar cycloaddition catalyzed by acetic acid is reported.
A vortex-assisted emulsification microextraction (VAEME) procedure has been evaluated for the determination of ten personal care products (PCPs), including seven preservatives (parabens), two UV filters (benzophenones), and one disinfectant (triclosan), in environmental waters. The method is utilized in combination with ultra-high performance liquid chromatography (UHPLC) and UV detection. The liquid-phase microextraction method results quite simple because it only needs one extractant solvent (200 µL of trichloromethane under optimum conditions) and it completely avoids the use of any dispersive solvent neither surfactants to help the emulsification. The optimized method ensures the correct emulsification by simple application of 3 min of vortex to 8 mL of aqueous sample at pH 5 containing 15% (w/v) of sodium chloride, followed by centrifugation (5 min at 3500 rpm), droplet sampling using a syringe, droplet solvent evaporation, and reconstitution with 100 µL of a mixture of acetonitrile:water (35:65, v/v) before UHPLC injection. The overall extraction time is roughly 10 min, and the chromatographic time ~12 min. The optimized method was validated, presenting average relative recoveries of 112%, average real extraction efficiencies of 82.7%, inter-day precision values with relative standard deviation (RSD, in %, for n = 9) values lower than 10%, and enrichment factors between ~20 and ~100, for a spiked level of 3.75 µg•L‒1. Limits of detection down to 0.03 µg•L‒1 were also obtained. The method satisfactory performed with environmental water samples with different nature and complexity.
The increasing production and consumption of Personal Care Products (PCPs), containing UV-filters and musk fragrances, has led to its widespread presence in the aquatic environment which can cause harmful effects to the aquatic organisms due to its intrinsic toxicity. This study aims to evaluate the degree of contamination of wild mussels along the entire Portuguese coastline, continually exposed in their habitat to different contaminants. For this purpose, approximately 1000 mussel specimens were sampled during one year in seven different locations, along the Portuguese coastline. Simultaneous quantification of five UV-filters and seven musks in mussels was achieved by a Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure combined with dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography with mass spectrometry (GC–MS) analysis.
Ten out of the twelve target analytes were found in the analysed samples, highlighting the presence of AHTN (tonalide), EHS (2-ethylhexylsalicylate) and EHMC (2-ethylhexyl 4-methoxycinnamate) in all positive samples (93%).
Overall, the results obtained indicate a widespread contamination of wild mussels along Portuguese coastline, all over the year. UV-filters were more frequently detected (90%) than musk fragrances (70%) and also quantified at higher levels, with average total concentrations reaching 1155.8 ng/g (dw) against 397.7 ng/g (dw) respectively. A high correlation was observed between the most densely populated and industrialized locations and the higher levels of musks and UV-filters found. In other hand, lower levels of PCPs were found in protected areas. As expected, an increase in UV-filters levels was observed after the summer, likely due to the intense period of recreational activities.
Benzophenones (BPs) family is one of the most frequently used groups of UV-filters. However, it has been reported by different authors that this kind of chemical compounds could be associated with some endocrine disrupting activity, genotoxicity and reproductive toxicity. In addition, different studies have evidenced the presence of BPs in several environmental matrices, indicating that conventional technologies of water treatment are not able to remove them, which generates the necessity of evaluating new alternatives of remediation. In this way, the main objective of this paper was to consider the potential removal of the benzophenone-type compounds, Benzophenone-1 and Benzophenone-2 in aqueous solutions using photo-Fenton under simulated sunlight radiation. Effects of different operational parameters, including H2O2 and Fe2+ initial concentrations, on pollutants elimination were assessed, and conditions that allow to get higher degradation rates were established. In general, results indicated that evaluated photo-catalytic system is able to remove completely the studied benzophenones, and to increase the samples biodegradability after a notable reduction of the organic carbon present in the solutions. Additionally, the identification of some of the reaction byproducts showed that hydroxylation of the substrates molecules is one of the main stages that conduct to its elimination under the evaluated experimental conditions.
The study investigated the occurrence and fate of seven benzophenone-type UV filters (i.e., 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2’,4,4’-tetrahydroxybenzophenone (2,2’,4,4’OH-BP), 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,2’-Dihydroxy-4,4’-dimethoxybenzophenone (2,2’OH-4,4'MeO-BP), 2,2’-Dihydroxy-4-methoxybenzophenone (2,2’OH-4MeO-BP), 4-hydroxybenzophenone (4OH-BP) and 4,4’-dihyroxybenzophenone (4DHB)) in a tropical urban watershed consisting of five major tributaries that discharge into a well-managed basin. Total benzophenone concentrations (∑▒C_BPs ) varied from 19 to 230.8 ng L-1 in overlying bulk water, 48 to 115 ng L-1 in pore water, 295 to 5813 ng g-1 dry weight (d.w.) in suspended solids, and 6 to 37 ng g-1 d.w. in surficial sediments, respectively. The tributaries (∑▒C_BPs : 19-231 ng L-1) were the main source of benzophenone compounds entering the basin (∑▒C_BPs : 20-81 ng L-1). In the water column, the vertical concentration profile in the aqueous phase was uniform while concentrations in the suspended solids decreased with depth. Different distribution profiles were also identified for benzophenones in suspended solids and sediments. A preliminary risk assessment suggested that the seven BPs were unlikely to pose ecotoxicological risks to local aquatic organisms except for 2OH-4MeO-BP in the case of an intermittent release.
The goals of this study were to bring forward new data and insights into the effect of activation methods, operational variables and reaction pathways during sulfate radicals-based oxidation of benzophenone-3 (BP-3) in aqueous solution. Heat, transition metal ions (Fe2+, Cu2+, Co2+), UV and visible light irradiation were used to activate persulfate (PS) to degrade BP-3. The results showed that these three activation methods can remarkably enhance BP-3 removal efficiency. Under the conditions of [BP-3]0: [PS]0 = 1: 500, pH = 7.0, and 40 °C, complete removal of BP-3 (1.31 μM) was observed in 3 h. In the pH range of 3.0-9.0, the degradation of BP-3 decreased with increasing pH. Increasing the PS dosage accelerated the reaction, while the presence of humic acid (HA) significantly inhibited the efficiency of BP-3 removal. Based on electron paramagnetic resonance (EPR) and radical quenching studies, sulfate and hydroxyl radicals contributed to the oxidation process. According to the evolution of BP-3 and its 7 by-products, as well as frontier electron densities (FED) calculation, two routes were proposed involving hydroxylation, demethylation and direct oxidation. On the whole, this work is a unique contribution to the systematic elucidation of BP-3 removal by PS.
In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species - mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice - were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs - EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values.
Benzophenone-2 (BP-2) is an important type of UV filter that has been widely used and detected in the aquatic environment with greater estrogenic toxicity. In our work, the removal of BP-2 with the initial concentration of 25 mg L⁻¹ was first carried out by ozone at different pH (ranging from pH 3.0 to 11.0), and we found a positive correlation between the pH values and the degradation efficiency of BP-2, among which the more rapid removal of BP-2 in alkaline condition was observed than acidic and neutral conditions. For the influence of aqueous humic acid (HA, the concentration ranged from 0 ppm to 100 ppm), the degradation rate of BP-2 by ozonation was first increased with the growth of humic acid concentration (from 0 ppm to 5 ppm), reaching to maximum at 5 ppm of HA and subsequently decreased with the growth of HA concentration (from 5 ppm to 100 ppm). Fourteen intermediate products in the ozonation process were distinguished by an electrospray time-of-flight mass spectrometer and then two degradation pathways were proposed. Through the theoretical calculation, we found the carbanyl group of BP-2 has the most reactivity to be easily attacked by ozone, providing us guides and theoretical basis on the supposed intermediate products. Furthermore, the P. phosphoreum acute toxicity test was conducted to evaluate the potential toxicity during the ozonation process.
UV filters (UV-Fs) constitute a heterogeneous group of chemicals used as protection against the effects of UV radiation, widely used in all sort of goods and ubiquitous in the environment. The presence of these chemicals in fish is a matter of concern, because many UV-Fs display hormonal activity. In this study, muscle, gills, and liver from 11 Mugil liza individuals from the highly urbanized Guanabara Bay (Rio de Janeiro, Brazil) were analysed in order to detect eight UV-Fs and metabolites (4-dihydroxybenzophenone [BP1] (2-hydroxy-4-methoxybenzophenone [BP3], 4-methylbenzylidiene camphor [4MBC], ethylhexyl methoxycinnamate [EHMC], ethylhexyl dimethyl p-aminobenzoic acid [ODPABA], octocrylene [OC], 4-hydroxybenzophenone [4HB], and 4,4'-dihydroxybenzophenone [4DHB]) using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Results showed that both target UV-Fs and metabolites were ubiquitous in the analysed tissues. Lower concentrations were observed in muscle and gills (3.07-31.6ngg(-1) dry weight (dw)), whereas in liver significant amounts of metabolites (5.47-451ngg(-1) dw) were present. With the concentrations determined in the fish, an estimation of the daily intake revealed that consumption of muscle in the diet represent from 0.3 to 15.2ng UV-Fs (kg body weight(-1)) d(-1), higher than those reported in fish for selected persistent organic pollutants (POPs).
This study is focused on the Guadalete River basin (SW, Spain), where extreme weather conditions have become common, with and alternation between periods of drought and extreme rainfall events. Combined sewer overflows (CSOs) occur when heavy rainfall events exceed the capacity of the wastewater treatment plants (WWTP), as well as pollution episodes in parts of the basin due to uncontrolled sewage spills and the use of reclaimed water and sludge from the local WWTP. The sampling was carried out along two seasons and three campaigns during dry (March 2007) and extreme rainfall (April and December 2010) in the Guadalete River, alluvial aquifer and Jerez de la Frontera aquifer. Results showed minimum concentrations for synthetic surfactants in groundwater (< 37.4 μg·L− 1) during the first campaign (dry weather conditions), whereas groundwater contaminants increased in December 2010 as the heavy rainfall caused the river to overflow. In surface water, surfactant concentrations showed similar trends to groundwater observations. In addition to surfactants, pharmaceuticals and personal care products (PPCPs) were analyzed in the third campaign, 22 of which were detected in surface waters. Two fragrances (OTNE and galaxolide) and one analgesic/anti-inflammatory (ibuprofen) were the most abundant PPCPs (up to 6540, 2748 and 1747 ng·L− 1, respectively). Regarding groundwater, most PPCPs were detected in Jerez de la Frontera aquifer, where a synthetic fragrance (OTNE) was predominant (up to 1285 ng·L− 1).
Ultraviolet-filters (UV-filters) and estrogens have attracted increased attention as contaminants of emerging concern (CECs) due to their widespread occurrence in the environment. Most of these CECs are hydrophobic and have the potential to accumulate in aquatic organisms. To date, co-analysis of UV-filters and estrogens has not been reported due, in part, to the complex environmental matrices. Here, a multi-residue method has been developed for simultaneous determination of five UV-filters and three estrogens in tissue from aquatic and marine organisms. The procedure involved a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with a novel reverse-solid-phase extraction (reverse-SPE) cleanup in place of dispersive-SPE, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. The tissue mass, acetonitrile content, and salt conditions for QuEChERS extraction, along with the reverse-SPE cartridge material and elution conditions, were thoroughly investigated and optimized. Five UV-filters (i.e., 3-(4-methylbenzylidene) camphor, benzophenone-3, ethylhexylmethoxycinnamate, homosalate, and octocrylene) and three estrogens (i.e., estrone, 17β-estradiol, and 17α-ethinylestradiol) were simultaneously analyzed by taking advantage of wrong-way-round ionization in LC-MS/MS. The optimized analytical protocol exhibited good recoveries (> 80%) for target compounds and enabled their detection at concentrations as low as 0.2 ng/g in 50 mg tissue samples. The method was applied to determine concentrations of target analytes in four invertebrates (i.e., Orconectes virilis, Procambarus clarkii, Crassostrea virginica, and Ischadium recurvum). All eight target analytes were detected at least once in the tissue samples, with the highest concentration being 399 ng/g of homosalate in O. virilis. These results highlight the ubiquitous bioaccumulation of CECs in aquatic and marine invertebrates.
Little is known with regard to the occurrence of potentially toxic chemicals in textiles and clothes. In this study, 77 textiles and infant clothing pieces were analyzed for the determination of bisphenols including bisphenol A (BPA) and bisphenol S (BPS), benzophenones, bisphenol A diglycidyl ethers (BADGEs), and novolac glycidyl ethers (NOGEs). BPA and BPS occurred in 82% and 53% of the textile samples, respectively, and at mean concentrations of 366 and 15 ng/g, respectively. Benzophenone-3 (BP3) occurred in 70% of the samples at a mean concentration of 11.3 ng/g. Among 11 BADGEs and NOGEs analyzed, BFDGE was the predominant compound, with a mean concentration of 13.6 ng/g. Concentrations of target chemicals were assessed by fabric type, color, and uses. Socks contained the highest concentrations of BPA (mean: 1,810 ng/g) with concentrations as high as 13,300 ng/g in a 97% polyester fabric marketed for infants. Calculated dermal exposure dose to BPA by infants via textiles was as high as 7,280 pg/kg-bw/d. This is the first study to report the occurrence of, and exposure to, BPA BPS, BADGEs, and NOGEs in textiles and clothing.
Organic ultraviolet (UV) filters are widely used in personal care products and occur ubiquitously in the aquatic environment. In this study, concentrations of seven commonly used organic UV filters were determined in seawater, sediment and five coral species collected from the eastern Pearl River Estuary of South China Sea. Five compounds, benzophenone-1, -3 and -8 (BP-1, -3 and -8), octocrylene (OC) and octyl dimethyl-p-aminobenzoic acid (ODPABA), were detected in the coral tissues with the highest detection frequencies (>65%) and concentrations (31.8 ? 8.6 and 24.7 ? 10.6 ng/g ww, respectively) found for BP-3 and BP-8. Significantly higher concentrations of BP-3 were observed in coral tissues in the wet season, indicating that higher inputs of sunscreen agents could be attributed to the increased coastal recreational activities. Accumulation of UV filters was only observed in soft coral tissues with bioaccumulation factors (log10-values) ranging from 2.21 to 3.01. The results of a preliminary risk assessment indicated that over 20% of coral samples from the study sites contained BP-3 concentrations exceeding the threshold values for causing larval deformities and mortality in the worst-case scenario. Higher probabilities of negative impacts of BP-3 on coral communities are predicted to occur in wet season.
Bioaccumulation and trophic transfer in ecosystems is an important criterion for assessing environmental risks of contaminants. This study investigated bioaccumulation and biomagnification of 13 organic ultraviolet absorbents (UVAs) in marine wildlife organisms in the Pearl River Estuary, South China Sea. The UVAs could accumulate in the organisms with biota - sediment accumulation factors (BSAF) of 0.003–2.152. UV531 was the most abundant and showed the highest tendency to accumulate in the organisms with a median BSAF of 1.105. The UVAs demonstrated species - and compound-specific accumulation in the marine organism. Fishes showed significantly higher capability than the cephalopods and crustaceans in accumulation of the UVAs. Habitat did not demonstrate obvious impact on accumulation of the UVA. On the other hand, benzophenone-3, UV328, and UV234 showed significantly higher concentration in the detritus feeding fishes than carnivorous and planktivorous fishes, suggesting governing effect of dietary habits of the organisms on bioaccumulation of these UVAs. Direct uptake from growth media was a significant exposure pathway of the organisms to the UVAs. The estimated trophic magnification factors and biomagnification factors revealed that UV329, UV531, and octocrylene could potentially biomagnify in the marine food web.
Organic UV-filters are key ingredients found in sunscreens, cosmetics and plastic goods. Concerns have been raised about potential ecological and human health effects of certain organic UV filters that are currently FDA approved for use in the United States. Here, we investigate the photochemical fate of two of these compounds, oxybenzone and sulisobenzone. Both oxybenzone and sulisobenzone have previously been detected in surface waters, seawater, and treated wastewater effluent. Direct photolysis is found to be unimportant for these compounds, however, enhanced photodegradation of oxybenzone and sulisobenzone was observed under simulated solar irradiation in solutions of International Humic Substance Society standards (Pony Lake fulvic acid and Suwannee River Natural Organic Matter), filtered wastewater effluent (Southerly Wastewater Treatment Plant in Lockbourne, OH), and Scioto River water (Columbus, OH) at pH 7. Quenching experiments with isopropanol revealed that the main pathway for degradation appears to be reaction with the hydroxyl radical (OH). Observed degradation rates were 2–3 times slower than estimates calculated using literature reported second-order rate constants and measured hydroxyl radical steady-state concentrations for SRNOM, PLFA and Scioto waters. The Southerly sample, however, exhibited nearly identical expected and observed rate constants, which we take to indicate the presence of unidentified reactive species that can react with oxybenzone and sulisobenzone. Values obtained in this work were used to calculate second-order rate constants for oxybenzone and sulisobenzone with the hydroxyl radical, as well as to estimate environmental half-lives for these compounds. Near surface 24-hour averaged half-lives of 3.0 and 4.0 days were calculated for oxybenzone and sulisobenzone, respectively. When extrapolated to an environmentally representative water column, these same 24-hour averaged half-lives increased to 2.4 and 3.5 years, respectively.
Marine echinoderms are filter-feeding invertebrates widely distributed along the coasts, and which are therefore extensively exposed to anthropogenic xenobiotics. They can serve as good sentinels for monitoring a large variety of contaminants in marine ecosystems. In this context, a multi-residue analytical method has been validated and applied to Holothuria tubulosa specimens and marine sediments for the determination of 36 organic compounds, which belong to some of the most problematic groups of emerging and priority pollutants (perfluoroalkyl compounds, estrogens, parabens, benzophenones, plasticizers, surfactants, brominated flame retardants and alkylphenols). Lyophilization of samples prior to solvent extraction and clean-up of extracts with C18, followed by liquid chromatography–tandem mass spectrometry analysis, is proposed. A Box–Behnken design was used for optimization of the most influential variables affecting the extraction and clean-up steps. For validation, matrix-matched calibration and recovery assay were applied. Linearity (% r²) higher than 99%, recoveries between 80 and 114% (except in LAS and NP1EO), RSD (precision) lower than 15% and limits of quantification between 0.03 and 12.5 ng g⁻¹ dry weight (d.w.) were achieved. The method was applied to nine samples of Holothuria collected along the coast of Granada (Spain), and to marine sediments around the animals. The results demonstrated high bioaccumulation of certain pollutants. A total of 25 out of the 36 studied compounds were quantified, being surfactants, alkylphenols, perfluoroalkyl compounds, triclocarban and parabens the most frequently detected. Nonylphenol was found in the highest concentration (340 and 323 ng g⁻¹ d.w. in sediment and Holothuria samples, respectively).
A methodology based on solid-phase-microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in water. The extraction parameters (the extraction mode and temperature, the fibre coating, and the addition of salt) were optimised by means of experimental designs in order to select the best extraction conditions. The final proposed conditions were 10 mL of water sample with 35% NaCl added, extracted in the headspace mode with a polyacrylate (PA) fibre at 100 °C for 20 minutes. The SPME-GC-MS/MS method was validated in terms of linearity (R² ≥ 0.9937), accuracy and precision, obtaining LODs in the range of 0.068-12 ng L⁻¹. The validated methodology was then applied to the analysis of different bathing water samples including sea, river, spa, swimming pool, and aquapark water, allowing the detection of 10 of the 14 target compounds; some of them were found at concentrations up to 692 ng mL⁻¹.
UV filters are a class of emerging contaminants that are widely used in personal care products (PCPs) and that can be detected at low concentrations in the aquatic environment (ngL(-1)). Sensitive modern analytical methods are then mandatory to accurately analyze them. A methodology based on solid-phase-microextraction (SPME), considered as a 'Green Chemistry' technique, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in environmental and recreational waters. In-vial low-cost derivatization was carried out to improve chromatographic performance of phenolic compounds. The extraction parameters (fiber coating, extraction mode, and salt addition) were optimized by means of experimental designs in order to achieve reliable conditions. Finally, the SPME-GC-MS/MS method was validated in terms of linearity, accuracy and precision with LODs in the low ngL(-1) level. Its application to the analysis of 28 different samples including sea, river, spa, swimming pool, and aquapark waters, enabled the detection of 11 target UV filters at concentration levels up to 540μgL(-1), highlighting the presence of OCR in all analyzed samples and of 2EHMC (proposed to be considered as priority pollutant) in 79% of them.
The present study focused on the kinetics, transformation pathways and toxicity of several benzophenone-type ultraviolet filters (BPs) during the water chlorination disinfection process. The transformation kinetics of the studied three BPs was found to be second-order reaction, which was dependent on the concentration of BPs and chlorine. The second-order rate constants increased from 86.7 to 975 M−1 s−1 for oxybenzone, 49.6 to 261.7 M−1 s−1 for 4-hydroxybenzophenone and 51.7 to 540 M−1 s−1 for 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid with the increasing pH value from 6 to 8 of the chlorination disinfection condition. Then the transformation products (TPs) of these BPs were identified by HPLC-QTof analysis. Several transformation pathways, including electrophilic substitution, methoxyl substitution, ketone groups oxidation, hydrolysis, decarboxylation and ring cleavage reaction, were speculated to participate in the chlorination transformation process. Finally, according to the toxicity experiment on luminescent bacteria, photobacterium phosphoreum, enhanced toxicity was observed for almost all the TPs of the studied BPs except for 2,2′-dihydroxy-4,4′-dimethoxybenzophenone; it suggested the formation of TPs with more toxic than the parent compounds during the chlorination process. The present study provided a foundation to understand the transformation of BPs during chlorination disinfection process, and was of great significance to the drinking water safety.
An accurate and sensitive method for the determination of selected EDCs in soil and compost from wastewater treatment plants is developed and validated. Five parabens, six benzophenone-UV filters and the antibacterials triclosan and triclocarban were selected as target analytes. The parameters for ultrasound-assisted extraction were thoroughly optimized. After extraction, the analytes were detected and quantified using ultra-high performance liquid chromatography tandem mass spectrometry. Ethylparaben (ring-13C6 labelled) and deuterated benzophenone (BP-d10) were used as internal standards. The method was validated using matrix-matched calibration and recovery assays with spiked samples. The limits of detection ranged from 0.03 to 0.40 ng g-1 and the limits of quantification from 0.1 to 1.0 ng g-1, while precision in terms of relative standard deviation was between 9% and 21%. Recovery rates ranged from 83% to 107%. The validated method was applied for the study of the behavior of the selected compounds in agricultural soils treated and un-treated with compost from WWTP. A lixiviation study was developed in both agricultural soil and treated soil and first order kinetic models of their disappearance at different depths are proposed. The application of organic composts in the soil leads to an increase of the disappearance rate of the studied compounds. The lixiviation study also shows the risk of pollution of groundwater aquifers after disposal or waste of these EDCs in agricultural soils is not high.
Oxybenzone (OBZ), known as Benzophenone-3, is a commonly used UV filter in sun tans and skin protectants, entering aquatic systems either directly during recreational activities or indirectly through wastewater treatment plants discharge. To study the potential degradation capacity of plants for OBZ in phytotreatment, a well-established hairy root culture (Armoracia rusticana) was treated with OBZ. More than 20% of spiked OBZ (100μM) was eliminated from the medium by hairy roots after 3h of exposure. Two metabolites were identified as oxybenzone-glucoside (OBZ-Glu) and oxybenzone-(6-O-malonyl)-glucoside (OBZ-Mal-Glu) by LC-MS/MS and TOF-MS. Formation of these metabolites was confirmed by enzymatic synthesis, as well as enzymatic and alkaline hydrolysis. Incubation with O-glucosyltransferase (O-GT) extracted from roots formed OBZ-Glu; whereas β-d-Glucosidase hydrolyzed OBZ-Glu. However, alkaline hydrolysis led to cleavage of OBZ-Mal-Glu and yielded OBZ-Glu. In the hairy root culture, an excretion of OBZ-Glu into the growth medium was observed while the corresponding OBZ-Mal-Glu remained stored in root cells over the incubation time. We propose that metabolism of oxybenzone in plants involves initial conjugation with glucose to form OBZ-Glu followed by malonylation to yield OBZ-Mal-Glu. To our best knowledge this first finding presenting the potential of plants to degrade benzophenone type UV filters by phytoremediation.
Benzophenone-3 (BP3) is one of the most used UV filters. Its disruptive effect on the endocrine system of different living beings has been demonstrated by several research groups. Present work addresses on a photocatalytic degradation of BP3 using particles of titanium dioxide in aqueous solutions considering the effect of operating parameters such as pH, catalyst and pollutant initial concentrations, and the presence of hydrogen peroxide, acetonitrile and isopropanol in the solution. In this way, a face centered, central composite design was carried out for the identification of significant factors or interactions that allow the determination of the conditions under which the pollutant suffers the highest rates of degradation. A solution initial pH of 9.0, a TiO2 concentration of 1.184 g L-1 and an H2O2 concentration of 128.069 mg L-1 were established as the optimal conditions for the substrate removal. In aqueous solutions and low concentrations of the pollutant (<2 mg L-1) photocatalytic degradation followed a pseudo-first order kinetics. After 300 min of treatment, ~67% of the dissolved organic carbon was removed, which together with a reduction in toxicity and an increase in biodegradability confirmed that photocatalysis with TiO2 is a potential method to remove BP3 from water. Additionally, tests using acetonitrile as solvent and isopropanol as hydroxyl radical (OH.) scavenger suggested that, OH. was the main agent responsible of substrate degradation. Finally, ten process by-products were identified and a degradation route was proposed.
The aim of this study was to assess the impact of chlorination on the degradation of one of the most commonly used UV filters (benzophenone-3 (BP3)) and the effects of bromide and ammonia on the kinetics of BP3 elimination. Bromide and ammonia are rapidly converted to bromine and chloramines during chlorination. At first, the rate constants of chlorine, bromine and monochloramine with BP3 were determined at various pH levels. BP3 was found to react rapidly with chlorine and bromine, with values of apparent second order rate constants equal to 1.25(± 0.14) × 103 M-1.s-1 and 4.04(±0.54) × 106 M-1.s-1 at pH 8.5 for kChlorine/BP3 and kBromine/BP3, respectively, whereas low monochloramine reactivity was observed (k_(NH_2 Cl/BP3)=0.112 M-1.s-1). To assess the impact of the inorganic content of water on BP3 degradation, chlorination experiments with different added concentrations of bromide and/or ammonia were conducted. Under these conditions, BP3 degradation was found to be enhanced in the presence of bromide due to the formation of bromine, whereas it was inhibited in the presence of ammonia. However, the results obtained were pH dependant. Finally, a kinetic model considering 18 reactions was developed using Copasi® to estimate BP3 degradation during chlorination in the presence of bromide and ammonia.
The occurrence and distribution of eight UV filters benzophenone (BP), benzophenone-3 (BP-3), ethylhexyl methoxy cinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA), 2-ethylhexyl salicylate (EHS), isoamyl benzoate, and benzyl cinnamate in eleven sites among three rivers, five sewage treatment plants (STPs), and four wastewater treatment plants (WWTPs) located in different parts of Korea was investigated. The total concentrations of UV filters in the three sampled seasons were 62.9-412ngL(-1) (river), 417-5055ngL(-1) (STP influent), 108-2201ngL(-1) (STP effluent), 122-4154ngL(-1) (WWTP influent), and 120-849ngL(-1) (WWTP effluent). The concentration of the target pollutants in the influent of the treatment systems was directly proportional to the resident population density. A seasonal increase of >27% was observed in the total concentration of the UV filters in the rivers and influents of the treatment plants (TPs) during summer. BP, BP-3, EHMC, 4-MBC, and EHS were the most dominant, showing a distinct distribution pattern that was dependent on the effectiveness of the treatment process and properties of each compound. The concentrations of the UV filters were higher in the TPs influents than in the rivers, and the most dominant UV filters in the rivers were those with low removal rate. Although biological treatment processes favored the removal of the UV filter compounds in the TPs, complete removal was not achieved before discharge into the rivers.
UV-filters are a group of compounds which have been massively used in the past years due to the recent concerns with sunburns, premature skin ageing and the risk of developing skin cancer, related to sun exposure. At the moment, these compounds have been identified by the scientific community as emerging pollutants, due to their persistence in the environment, potential to accumulate in biota and potential threat as endocrine disruptors. At some point, the majority of sunscreens will find their way into wastewater (due to bathing and washing activities) and because wastewater treatment plants (WWTPs) are not able to remove and/or degrade them, consequently they find their way into rivers, lakes and ocean, so it is not surprising that UV-filters are found in the environment. Therefore, wastewater treatment plants should be the focus of the scientific community aiming to better understand the fate of the UV-filters and develop new technologies to remove them from wastewater and sludge. This review, aims to provide the current state of the art in the occurrence and fate of UV-filters in wastewater treatment plants and how the technologies that are being used are successfully removing these compounds from both wastewater and sludge.
For the first time, an efficient and sensitive analytical method based on liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry (LC-QqLIT-MS/MS) was developed for the simultaneous determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in both plant (Sargassum fusiforme, porphyra, kelp) and animal (hairtail, yellow croaker, shrimp) seafood. The samples were extracted in methanol by pressurized liquid extraction (PLE), and the extracts were then cleaned up by mixed-mode cationic exchange (MCX) solid-phase extraction cartridges. Both isotope-labeled internal standards and matrix-matched calibration standards were used to alleviate and correct for the matrix effects, and the limits of quantification (LOQs) were 10.0 μg kg-1 for all target compounds. The average recoveries were in the range of 80.6-107.8% at three spiked concentration levels (10, 50 and 100 μg kg-1) with relative standard deviations (RSDs) below 8.5%. The results suggest that very limited contamination of these seven emerging contaminants, mainly associated with PCPs, occurred in these common seafoods.
This paper reports the results of an experimental work on sonochemical degradation of benzophenone-3 (BP3), one of the most commonly used ultraviolet (UV) filters whose disruptive effect on the endocrine system of various living beings has been demonstrated. Ultrasound irradiation is a promising advanced oxidation technology that has received considerable interest as an alternative for degradation of persistent organic pollutants through hydroxyl free radicals that are generated from the cavitation bubbles implosion. Taking into account the potential risk due to the presence of BP3 in the environment and its possible removal using ultrasound, the effect of operating parameters such us ultrasonic applied power, pollutant initial concentration, pH, the presence of gases (including ozone), inorganic anions and alcohols on the substrate removal was investigated. During sonochemical treatment, a higher pollutant degradation rate was achieved by increasing the power in a range of 40.2–80.1 W. Likewise, at lower benzophenone-3 initial concentrations, higher extents of degradation were observed, which could be explained by a heterogeneous kinetics model. Acidic pH enhanced the pollutant initial degradation by 21 %. Oxygen, ozone and bicarbonate ions affected positively the benzophenone-3 removal, while nitrogen, nitrate and chloride anions inhibited it. Measurements of concentration of hydroxyl free radicals indicated that by promoting OH. radical formation, the pollutant elimination rate can be increased.
A novel porous sponge-like zinc-zinc oxide (Zn-ZnO) coating was directly prepared on an etched stainless steel wire substrate as a solid-phase microextraction (SPME) fiber via previous electrodeposition of a robust ZnO coating. The scanning electron micrograph of the Zn-ZnO coated fiber exhibits a porous spongy nanostructure with a large surface area. The SPME performance of the prepared fiber was investigated for the concentration and determination of polycyclic aromatic hydrocarbons, phthalates and ultraviolet (UV) filters by high performance liquid chromatography coupled with UV detection (HPLC-UV). It was found that the porous sponge-like Zn-ZnO coating exhibited high extraction capability, good selectivity and rapid mass transfer for some UV filters. The main parameters affecting extraction performance were investigated and optimized. Under optimized conditions, the calibration graphs were linear over the range of 0.1-200 μg L-1. The limits of detection of the proposed method were 0.032-0.064 μg L-1 (S/N = 3). The single fiber repeatability varied from 5.5% to 7.2% and the fiber-to-fiber reproducibility ranged from 7.1% to 8.3% for the extraction of spiked water with 50 μg L-1 UV filters (n = 5). The established SPME-HPLC-UV method was successfully applied to the selective concentration and sensitive determination of target UV filters from real environmental water samples with recoveries from 80.3% to 99.2% at the spiking level of 5 μg L-1 and 50 μg L-1. The relative standard deviations were below 9.3%.
In the last decades, awareness regarding personal care products (PCP), i.e. synthetic organic chemicals frequently used in cosmetic and hygienic products, has become a forward-looking issue, due to their persistency in the environment and their potential multi-organ toxicity in both human and wildlife. Seafood is one of the most significant food commodities in the world and, certainly, one of the most prone to bioaccumulation of PCP, what can consequently lead to human exposure, especially for coastal population, where its consumption is more marked. The aim of this work was to evaluate the co-occurrence of musk fragrances and UV-filters in both seafood and macroalgae collected in different European hotspots (areas with high levels of pollution, highly populated and near wastewater treatment plants). Despite the fact that UV-filters were detected in three different kind of samples (mussel, mullet, and clam), in all cases they were below the limit of quantification. Galaxolide (HHCB) and tonalide (AHTN) were the musk fragrances most frequently detected and quantified in samples from the European hotspots. Cashmeran (DPMI) was also detected in most samples but only quantified in two of them (flounder/herring and mullet). The highest levels of HHCB and AHTN were found in mussels from Po estuary.
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UV-filters are a group of compounds designed mainly to protect skin against UVA and UVB radiation, but they are also included in plastics, furniture, etc., to protect products from light damage. Their massive use in sunscreens for skin protection has been increasing due to the awareness of the chronic and acute effects of UV radiation. Some organic UV-filters have raised significant concerns in the past few years for their continuous usage, persistent input and potential threat to ecological environment and human health. UV-filters end up in wastewater and because wastewater treatment plants are not efficient in removing them, lipophilic compounds tend to sorb onto sludge and hydrophilics end up in river water, contaminating the existing biota. To better understand the risk associated with UV-filters in the environment a thorough review regarding their physicochemical properties, toxicity and environmental degradation, analytical methods and their occurrence was conducted.
Due to the growing concern about human health effects of ultraviolet (UV) radiation, the use of UV filters has increased in recent decades. Unfortunately, some common UV filters are bioaccumulated in aquatic organisms and show a potential for estrogenic activity. The aim of the present study is to determine the presence of some UV filters in the coastal waters of six beaches around Gran Canaria Island as consequence of recreational seaside activities. Eight commonly used UV filters: benzophenone-3 (BP-3), octocrylene (OC), octyl-dimethyl-PABA (OD-PABA), ethylhexyl methoxy cinnamate (EHMC), homosalate (HMS), butyl methoxydibenzoyl methane (BMDBM), 4-methylbenzylidene camphor (4-MBC) and diethylamino hydroxybenzoyl hexyl benzoate (DHHB), were monitored and, with the exception of OD-PABA, all were detected in the samples collected. 99% of the samples showed some UV filters and concentration levels reached up to 3316.7ng/L for BP-3. Environmental risk assessment (ERA) approach showed risk quotients (RQ) higher than 10, which means that there is a significant potential for adverse effects, for 4-MBC and EHMC for those samples with highest levels of UV filters.
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Benzophenone-3 (2-hydroxy-4-methoxybenzophenone; BP-3) is widely used as sunscreen for protection of human skin and hair from damage by ultraviolet (UV) radiation. In this study, we examined the metabolism of BP-3 by rat and human liver microsomes, and the estrogenic and anti-androgenic activities of the metabolites. When BP-3 was incubated with rat liver microsomes in the presence of NADPH, 2,4,5-trihydroxybenzophenone (2,4,5-triOH BP) and 3-hydroxylated BP-3 (3-OH BP-3) were newly identified as metabolites, together with previously detected metabolites 5-hydroxylated BP-3 (5-OH BP-3), a 4-desmethylated metabolite (2,4-diOH BP) and 2,3,4-trihydroxybenzophenone (2,3,4-triOH BP). In studies with recombinant rat cytochrome P450, 3-OH BP-3 and 2,4,5-triOH BP were mainly formed by CYP1A1. BP-3 was also metabolized by human liver microsomes and CYP isoforms. In estrogen reporter (ER) assays using estrogen-responsive CHO cells, 2,4-diOH BP exhibited stronger estrogenic activity, 2,3,4-triOH BP exhibited similar activity, and 5-OH BP-3, 2,4,5-triOH BP and 3-OH BP-3 showed lower activity as compared to BP-3. Structural requirements for activity were investigated in a series of 14 BP-3 derivatives. When BP-3 was incubated with liver microsomes from untreated rats or phenobarbital-, 3-methylcholanthrene-, or acetone-treated rats in the presence of NADPH, estrogenic activity was increased. However, liver microsomes from dexamethasone-treated rats showed decreased estrogenic activity due to formation of inactive 5-OH BP-3 and reduced formation of active 2,4-diOH BP. Anti-androgenic activity of BP-3 was decreased after incubation with liver microsomes.
Copyright © 2014. Published by Elsevier Inc.
