Benzophenone-3 Research Articles

Biochemical Perturbations and Metabolic Derangements Induced by Benzophenone-3 at Environmentally Relevant Concentration in the Liver of Danio rerio

UV filters are used daily by millions of people. many wastewater treatments plants are ill-equipped to filter them properly. As a result, UV filters are progressively reaching the environment at an alarming level. Benzophenone-3(BP3) in particular, are toxic to all organisms. Its toxic effects include coral bleaching and interference with metabolic, enzymatic, and reproductive activities. The present study aims to assess the toxic impact of environmentally relevant concentration of BP3(44μg/l) on some selected biochemical variables in the liver tissue of Zebra fish on different exposure periods. The exposed fishes were shown to exhibit significant alterations in the carbohydrate, lipid and protein levels and their metabolism and elevated the level of transaminases in the hepatic tissue. The severity of derangement was slowly increased upon increasing exposure period and more significant at the 45th days of exposure. From our results, it may suggested that BP3 exposure at sub chronic periods even at the environmentally relevant concentration might induce intense biochemical alterations in the liver of D.rerio.

Benzophenone-2 exerts reproductive toxicity in male rats

Benzophenone derivatives such as benzophenone-2 (BP-2) belong to the group of endocrine disrupting compounds (EDCs). Increased exposure to EDCs is considered to be an important factor behind the decline of human fertility. The main aim of the present study was to determine the effect of BP-2 on testicular function specified by sperm analysis, the level of sex hormones and their receptors. Since BP-2 has been shown to activate the immune system, another aim of the research was to verify the hypothesis that the immune system may be contributing to the testis toxicity of this compound and for this purpose changes in macrophage and lymphocyte populations in the testes were determined. BP-2 at a dose of 100 mg/kg was administered dermally, twice daily at a dose of 100 mg/kg for 4-weeks. It was shown that BP-2 reduced the number and motility of sperm and increased the number of sperm showing morphological changes. By determining the concentration of sex hormones, a significant decrease in testosterone levels and an increase in the blood levels of 17β-estradiol were demonstrated. Similar to the results obtained from the blood samples, testosterone levels in the testes were lowered, which could affect sperm parameters. The effect of BP-2 on lowering testosterone levels and the number of sperm cells may be due to immunoactivation in the testes, because it has been detected that this compound significantly decreased the number of the immunosuppressive resident testicular macrophages (TMs) (CD68-CD163+), but increased pro-inflammatory TMs with monocyte-like properties (CD68+CD163-).

Distribution of Nine Organic UV Filters along the Shore Next to the Harbor Canals in the Middle Pomeranian Region (Northern Poland)

Spatiotemporal changes in the concentration of UV filters were investigated along the shore according to increasing distance from breakwaters, from the shoreline, as well as according to seasonality in three locations of different anthropogenic pressures, involving those from cosmetic products being released during touristic activity. Nine organic UV filters (benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), octocrylene (OCR), 4-methoxy benzylidene camphor (4-MBC), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS), homosalate (HMS), and butyl methoxydibenzoylmethane (BMDM)) were determined in core sediments, and the range of determined concentrations above the limit of quantification was between 19.2 ng·kg−1 d.w. (HMS) and 539.5 μg·kg−1 d.w. (4-MBC). Unexpectedly, contrary to the level of anthropogenic pressure, the concentrations of four (BP-1, BP-2, BP-3, OCR) UV filters decreased in the following order: Darłówko > Ustka > Rowy. Higher concentrations of BP-1, BP-2, BP-3, and OCR were determined in spring than in summer and autumn. The maximal concentration of HMS and EHMC/EHS was found in the summer and in the autumn, respectively. BMDM was determined occasionally only in two samples collected in Ustka. The higher maximal concentration range of all UV filters was determined in core sediments taken from the eastern (539.5 μg·kg−1 d.w.) rather than from the western (11.3 μg·kg−1 d.w.) parts of the beaches. According to increasing distance from the breakwaters, higher concentrations of UV filters were determined in sites located up to 100 m away in all locations and seasons. Spatial variation in the concentration of UV filters was observed in profiles perpendicular to the water line. Typically, higher concentrations were determined at sites having contact with water, although incidentally, high concentrations were also noticed at sites located further into the beach. The Polish coast of the Baltic Sea is not free from organic UV filters, and expectations concerning the abundance of UV filters in a given location are far from recorded data due to the impact of hydro-technical treatments (i.e., stony and wooden breakwaters, artificial reefs, nourishment) and coastal littoral drift.

Toxicity assessment of binary mixtures of BP3 with 4-MBC (UV-filters), and BP3 with DEET (insect repellent) using the aquatic midge Chironomus riparius

Personal care products have various organic ultraviolet filters (UV filters) in their composition to increase protection against ultraviolet radiation. Some of these products also contain insect repellents in their formulations. Consequently, these compounds reach freshwater ecosystems, exposing aquatic organisms to a cocktail of anthropogenic contaminants. In this study, the joint effects of two most frequently detected UV filters (Benzophenone – 3 (BP3) and Enzacamene (4-MBC)) and joint effects of BP3 combined with an insect repellent (N, N diethyl-3-methylbenzamide – DEET) were evaluated using life-history traits of the aquatic midge Chironomus riparius such as emergence rate, time to emergence and imagoes body weight. The results showed synergistic effects between BP3 and 4-MBC for C. riparius emergence rate. Regarding the effects of BP3 and DEET mixture, our analysis suggests synergism in the case of males but antagonism in the case of females' time to emergence. Our results imply that the effects of UV filters present in sediments within chemical mixtures are complex and that the evaluation of effects using different life-history traits can yield different patterns of responses. This study demonstrates the importance of assessing the combined effects of pollutants used/found concomitantly in aquatic systems for a more accurate risk assessment, as individual chemical testing can underestimate the toxicity of organic UV filters.

Synergistic effects of permanganate and chlorination on the degradation of Benzophenone-3: Kinetics, mechanisms and toxicity evaluation

To obtain utilization efficiency of low permanganate (KMnO4), it is available to combine with other chemical agents. This work found the synergistic effects of adding KMnO4 and sodium hypochlorite (NaClO) simultaneously on the efficient degradation of benzophenone-3 (BP-3). The synergy factors of the combined method were increased with increasing concentrations of KMnO4 and NaClO. Neutral and alkaline conditions were more favorable for BP-3 removal. Methyl phenyl sulfoxide (PMSO) was used as the probe to detect high-valence Mn species (e.g., Mn(VI), Mn(V)). Results indicated that the reactivity of KMnO4 was improved by NaClO by increasing the content of high-valence Mn species. Cl- converted from NaClO was oxidized by KMnO4 to generate Cl2, also promoting the degradation of BP-3. The oxidative mechanisms of BP-3 in the system of KMnO4 coupling with NaClO (KMnO4/NaClO) mainly included oxidative ring-opening, carboxylation, Bayer-Villiger oxidation, electrophilic chlorination, hydroxylated reactions and cleavage, but oxidative ring-opening products were detected only in the combined system. Due to the reduced dosage of chlorine and the decreased toxicity in the combined process, KMnO4/NaClO decreased the environmental risk of the reaction process largely. Comprehensively analyzing the degradation efficiency and environmental risk in treatment of BP-3 by the combined process, KMnO4/NaClO oxidation is a promising technology for water treatment.

Association between environmental chemical exposure and albumin-to-creatinine ratio is modified by hypertension status in women of reproductive age

Chemicals have been identified as a potential risk factor of renal dysfunction. However, studies that consider both multiple chemicals and non-chemical risk factors, such as hypertension, are rare. In this study, we assessed the associations between exposure to several chemicals, including major metals, phthalates, and phenolic compounds, and the albumin-to-creatinine ratio (ACR). A group of Korean adult women in reproductive age (n = 438, aged between 20 and 49 years), who had previously been studied for association of several organic chemicals, was chosen for this purpose. We constructed multivariable linear regression models for individual chemicals and weighted-quantile sum (WQS) mixtures, by hypertension status. Among the study population, approximately 8.5% of the participants exhibited micro/macro-albuminuria (ACR ≥30 mg/g), and 18.5% and 3.9% exhibited prehypertension and hypertension, respectively. Blood cadmium and lead levels showed a stronger association with ACR only among women with prehypertension or hypertension. Among organic chemicals, depending on the statistial model, benzophenone-1 (BP-1) and mono(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP) showed a significant association regardless of hypertension status, but most associations disappeared in the (pre)hypertensive group. These findings clearly indicate that hypertension status can modify and may potentiate the association of environmental chemicals with ACR. Our observations suggest that low-level environmental pollutant exposure may have potential adverse effects on kidney function among general adult women. Considering the prevalence of prehypertension in the general population, efforts to reduce exposure to cadmium and lead are necessary among adult women to minimize the risk of adverse kidney function.

Biomarkers activity in Oreochromis niloticus under sub-chronic exposure to a UV filters ternary mixture

The behavior of organic UV filters in aquatic ecosystems and living organisms raises concern. For the first time, biochemical biomarkers were evaluated in the liver and brain of juvenile Oreochromis niloticus exposed to 0.001 and 0.5 mg L−1 of a benzophenone-3 (BP-3), octyl methoxycinnamate (EHMC), and octocrylene (OC) mixture for 29 days. Before the exposure, the stability of these UV filters was investigated using liquid chromatography. The experiment with aeration in the aquarium showed a high percentage of concentration reduction (%) after 24 h: 62 ± 2 for BP-3, 96 ± 6 for EHMC, and 88 ± 2 for OC versus 5 ± 4 for BP-3, 8 ± 7 for EHMC, and 2 ± 3 for OC when without aeration. These results defined the bioassay protocol. The stability of the filters concentrations after being stored in PET flasks and subjected to freezing and thawing cycles was also verified. In PET bottles, the BP-3, EHMC, and OC presented concentration reductions of 8 ± 1, 28 ± 7 and 25 ± 5 respectively, after 96 h storage and four freezing cycles. In falcon tubes the concentration reductions observed were 47 ± 2 for BP-3, >95 ± 1 for EHMC and 86 ± 2 for OC after 48 h and two cycles. The 29 days of sub-chronic exposure indicated the occurrence of oxidative stress through the enhanced lipid peroxidation (LPO) levels for the groups exposed to both bioassay concentrations. The catalase (CAT), glutathione-S-transferase (GST), and acetylcholinesterase (AChE) activities did not show significant alterations. The genetic adverse effects were analyzed in erythrocytes of fish exposed to 0.001 mg L−1 of the mixture by comet and micronucleus biomarkers and no significant damage was observed.

Trophic transfer of DDE, BP-3 and chlorpyrifos from microplastics to tissues in Dicentrarchus labrax

Microplastic pollution and associated chemical contaminants is a topic of growing interest. In recent years, the number of publications reporting the presence of microplastics (MPs) in marine organisms has increased exponentially. However, there is a gap in knowledge about the trophic transfer of contaminants from microplastics to animal tissues, as well as possible health effects. In this study we analyzed the trophic transfer and biomagnification of three chemical pollutants present in microplastics: dichlorodiphenyldichloroethylene (DDE-p,p’), benzophenone 3 (BP-3) and chlorpyrifos (CPS). The reference values used were concentrations found in environmental microplastics in the Canary Islands (minimum and maximum). European seabass (Dicentrarchus labrax) were fed for 60 days with 5 different treatments: A) feed; B) feed with chemical pollutants at maximum concentration; C) feed + 10 % virgin MPs; D) feed + 10 % MPs with chemical pollutants at minimum concentration; E) feed + 10 % MPs with chemical pollutants at maximum concentration. We detected trophic transfer of DDE-p,p’, CPS and BP-3 from the feed (treatment B) to the muscle and liver of fish. In the case of DDE-p,p’, transfer to liver and muscle was also observed in the treatments consisting of feed plus plastics with different levels of contamination (C, D and E). No effect of the experimental treatments on fish condition indices was observed.

A Simultaneous Determination of Benzophenone and Camphor UV-Filters, Together with Metabolites of Polycyclic Aromatic Hydrocarbons, in Human Urine

By monitoring biomarkers in urine, personal exposure to selected chemical substances can be assessed. In this paper, we describe the monitoring of 7 benzophenone and 2 camphor UV-filters and 11 metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) in 454 urine samples collected from mothers and new-borns from an industrial (Karvina) and reference area (Ceske Budejovice) over winter and summer seasons. The analytical method consisted of enzymatic hydrolysis, liquid–liquid extraction (ethyl acetate), purification by dispersive solid-phase extraction (Z-Sep sorbent) and ultra-high performance liquid chromatography coupled with tandem mass spectrometry. Benzophenone-1 (BP-1), naphthalen-2-ol (2-OH-NAP), fluoren-2-ol (2-OH-FLUO) and phenanthren-2-ol (2-OH-PHEN) were determined in all urine samples analysed. Benzophenone-3 (BP-3) and 2-OH-NAP were found at the highest concentrations (medians of 5.95- and 5.77-µg/g creatinine). Analytes 3-(4-methylbenzylidene)camphor (3-MBC), 3-benzylidenecamphor (3-BC), chrysen-6-ol (6-OH-CHRY) and benzo(a)pyrene-3-ol (3-OH-BaP) were not detected in any urine sample. Median concentrations of UV-filters and OH-PAHs were compared across regions in the Czech Republic and between mothers and their new-borns from different countries. The median concentrations of UV-filters measured in urine samples from new-borns in our study were similar to samples collected from Brazilian children and the concentrations of these compounds in mothers’ samples were comparable with the concentrations in Danish mothers. In the case of OH-PAHs, the median concentrations of these substances measured in urine samples from Czech new-borns were comparable to median concentrations of these compounds measured in new-born urine from our previous study, and the concentrations in urine collected from Czech mothers were comparable to those reported in Spanish women.

Biochemical responses of the mussel Perna perna after exposure to environmental concentrations of the UV filter Benzophenone-3

Personal care products, such as UV filters, are frequently present in aquatic ecosystems, but studies on their impact on marine organisms are still scarce. Here we addressed the effects of benzophenone-3 (BP-3) on the antioxidant status of Perna perna mussels exposed to concentrations of 0.1 and 3 μg.L−1 for 72 h and 7 days. Glutathione peroxidase (GPx), glutathione reductase (GR), glutathione S-transferase (GST), glucose-6-phosphate dehydrogenase (G6PDH) activity and lipoperoxidation (MDA) were evaluated in the gills. A significant reduction (p < 0.05) in the activity of G6PDH and GPx was observed after exposure for 7 days to 0.1 µg.L−1. However, no significant differences were observed in GST activity and MDA levels, independently of the exposure time. Principal component analysis (PCA) showed an association of BP-3 highest concentration with GR and MDA at 72 h and only with GR at 7 days of exposure. Similarly, the integrated biomarker response (IBR) demonstrated GR and MDA alterations. In conclusion, environmentally relevant concentrations of BP-3 altered antioxidant and auxiliary enzymes, which could cause long-term damage to P.perna mussels. The need to implement more efficient techniques in wastewater treatment systems is pointed out, especially in summer, when UV filters are used more frequently and abundantly.

Results of the Austrian Children's Biomonitoring Survey 2020 part A: Per- and polyfluorinated alkylated substances, bisphenols, parabens and other xenobiotics.

In 85 Austrian school children aged 6-10 years, two multi-analyte LC-MS/MS methods were used to study the concentrations of 33 chemical substances in urine, including per- and polyfluorinated alkylated substances (PFAS), bisphenols, parabens, benzophenones, triclosan, polycyclic aromatic hydrocarbon metabolites, and cotinine. Each of the children was exposed to 14-21 substances simultaneously. Correlations were found between compounds of the same and of divergent substance groups supporting the strong need to consider multiple exposures and mixture effects. Eight compounds, including perfluorohexanoic acid (PFHxA), perfluorononanoic acid (PFOA), methyl paraben (n-MeP), ethyl paraben (n-EtP), propyl paraben (n-PrP), benzophenone-1 (BP-1), 2-naphthol, and 3-hydroxyphenanthrene were detected in all urine samples. In the PFAS group the medians of detectable substances ranged between <0.0005μg/l for perfluorononanoic acid (PFNA) and 0.004μg/l for PFHxA. For other environmental contaminants investigated, a maximum urinary level of 893μg/l was identified for n-MeP. The highest median value was 2.5μg/l for 2-naphthol. Daily intakes were calculated for bisphenol A (BPA), triclosan (TCS), and four parabens. These values did not exceed the tolerable or acceptable daily intakes currently in force. Based on a recently proposed TDI for BPA, daily intakes of all children exceeded this value. A cumulative risk assessment was conducted for four parabens not showing exceedances of acceptable exposures. The results demonstrate simultaneous exposure to several different chemicals, with the majority showing impact on the endocrine system being of particular concern with respect to mixture effects. Further assessments with a stronger focus on mixtures are warranted. The results also highlight the need of policy actions as foreseen in the EU Chemicals Strategy for Sustainability.

Determination of 12 typical personal care products in human urine samples by ultra performance liquid chromatography-tandem mass spectrometry

A rapid and sensitive method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 12 typical personal care products (PCPs) in human urine. These PCPs included five paraben preservatives (PBs), five benzophenone UV absorbers (BPs), and two antibacterial agents. Accordingly, 1 mL of the urine sample was mixed with 500 μL of β-glucuronidase-ammonium acetate buffer solution (enzymatic activities are 500 units/mL) and 75 μL of a mixed internal standard working solution (internal standard contents are 7.5 ng), followed by enzymatic hydrolysis overnight (≥16 h) at 37 ℃ in a water bath. The 12 targeted analytes were enriched and cleaned up using an Oasis HLB solid phase extraction column. Separation was performed on an Acquity BEH C18 column (100 mm×2.1 mm, 1.7 μm) using an acetonitrile-water system as the mobile phase, in negative electrospray ionization (ESI-) multiple reaction monitoring (MRM) mode, for target detection and stable isotope internal standard quantification. The optimal MS conditions were established by optimizing the instrument parameters and comparing two analytical columns (Acquity BEH C18 and Acquity UPLC HSS T3) as well as different types of mobile phases (methanol or acetonitrile as the organic phase) to achieve better chromatographic separation. In order to obtain higher enzymatic and extraction efficiency, different enzymatic conditions, solid phase extraction columns, and elution conditions were investigated. The final results showed that methyl parabens (MeP), benzophenone-3 (BP-3), and triclosan (TCS) showed good linearities in the ranges of 4.00-800, 4.00-800 and 5.00-200 μg/L, respectively, the other targeted compounds showed good linearities in the ranges of 1.00-200 μg/L. The correlation coefficients were all greater than 0.999. The method detection limits (MDLs) were in the range of 0.06-1.09 μg/L, and the method quantification limits (MQLs) ranged from 0.08 to 3.63 μg/L. At three spiked levels, the average recoveries of the 12 targeted analytes ranged from 89.5% to 111.8%. The intra-day and inter-day precisions were 3.7%-8.9% and 2.0%-10.6%, respectively. The results of the matrix effect assessment showed that MeP, ethyl paraben (EtP), and benzophenone-2 (BP-2) exhibited strong matrix effects (26.7%-103.8%); propyl paraben (PrP) exhibited moderate matrix effects (79.2%-112.0%); and the other eight target analytes exhibited weak matrix effects (83.3%-113.8%). The matrix effects of the 12 targeted analytes after correction using the stable isotopic internal standard method ranged from 91.9% to 110.1%. The developed method was successfully applied to the determination of the 12 PCPs in 127 urine samples. Ten typical PCPs were detected, with the overall detection rates ranging from 1.7% to 99.7%, except for benzyl paraben (BzP) and benzophenone-8 (BP-8). The results revealed that the population in this area was widely exposed to PCPs, especially MeP, EtP and PrP; the detection rates and concentrations of these PCPs were found to be very high. Our analytical method is simple and sensitive, and it is expected to be an effective tool for biomonitoring PCPs in human urine samples as part of environmental health studies.

Comparison of developmental toxicity of benzophenone-3 and its metabolite benzophenone-8 in zebrafish

Benzophenone-3 (BP-3) as one of frequently used organic UV filters has been considered an emerging pollutant due to its toxicities. Benzophenone-8 (BP-8) is one of the main metabolites of BP-3 in organisms. Current reports show that BP-8 may be more toxic than BP-3. However, difference of their toxicities on embryonic development has rarely been reported. In this study, zebrafish embryos were chosen as the target organism to explore the developmental toxicities of BP-3 and BP-8. Non-targeted metabolomic analysis was performed to compare their modes of action. Results showed that BP-8 exposures led to higher bioaccumulation and lower hatching rate of zebrafish larvae than BP-3. Both BP-8 and BP-3 exposures caused behavioral abnormalities of zebrafish larvae, but no significant difference was found between them. At the metabolome level, 1 μg/L BP-3 and 1 μg/L BP-8 exposures altered neuroactive ligand-receptor interaction pathway and FoxO signaling pathway, respectively, which might be involved in the abnormal behaviors in zebrafish larvae. For higher exposure groups (30 and 300 μg/L), both BP-3 and BP-8 exposures changed metabolism of cofactors and vitamins of zebrafish larvae. Exposure of BP-3 altered the metabolism by pantothenate and CoA biosynthesis pathway, while BP-8 exposure changed riboflavin metabolism and folate biosynthesis. The above results indicated different modes of action of BP-3 and BP-8 in zebrafish embryonic development. This study sheds new light to biological hazards of BP-3 due to its metabolism in aquatic organisms.

Embryonic benzophenone-3 exposure inhibited fertility in later-life female zebrafish and altered developmental morphology in offspring embryos.

Benzophenone-3 (BP3), an organic UV filter widely used in personal care products, is ubiquitous in aquatic environments. Previous studies have shown that BP3 can interfere with oocytes development in the ovary. The current study was conducted to evaluate the effects of embryonic BP3 exposure on reproductive outcomes in later life. Zebrafish embryos were exposed to different concentrations of BP3 (0, 1, 10, 100 μg/L) for 5 days in the developmental stage and subsequently fed for 4 months without any toxins. The body length, body weight, and ovary weight in F0 female adult zebrafish and morphology indices in F1 offspring embryos were measured. The reproductive behaviors of adult zebrafish were recorded by a digital camera. HE staining was used to estimate the development of oocytes and the proportion of different phases was calculated. qPCR was used to detect the expression levels of reproduction-related genes of the hypothalamic-pituitary-gonadal (HPG) axis. Our findings revealed that the body length and body weight were not changed with embryonic BP3 exposure, but BP3 exposure inhibited the development and maturation of ovaries in later-life female zebrafish, accompanied by an increased proportion of follicles in the primary growth and early vitellogenic stages, and a decline in the full-growth stage in ovaries. Meanwhile, reduced egg production, delayed hatching rate, altered somite count and increased mortality rate were observed at 100 μg/L in offspring embryos. Behavioral results showed that BP3 exposure reduced the frequency of chasing, touching, entering the spawning area, and the duration of fish entering the spawning area later in life, qPCR analysis showed that the expression levels of reproduction-related genes of the HPG axis were downregulated in females, following a decreasing trend in plasma E2 and 11-KT levels. These results suggested that embryonic BP3 exposure negatively affected the fertility of fish and the development of their offspring embryos, which may cause potential risks to aquatic ecosystems and human health.

Urinary concentration of selected nonpersistent endocrine disrupting chemicals—reproductive outcomes among women from a fertility clinic

Parabens and benzophenones are compounds widely used in cosmetics and personal care products. Although human exposure is widespread there is a limited number of epidemiological studies assessing the relationship between exposure to these chemicals and female reproductive health. The aim of the study is to explore the relationship between paraben and benzophenone concentrations and reproductive outcomes among women attending a fertility center. This prospective cohort included 450 women undergoing in vitro treatment (IVF) at fertility clinic in Poland. The validated gas chromatography ion-tap mass spectrometry to assess concentrations of parabens in urine (methyl (MP), ethyl (EP), propyl (PP), butyl paraben (BP)) and benzophenone-3 (BP-3) was used. To explore the relationship between concentrations of examined chemicals and reproductive outcomes (methaphase II (MII) oocyte yield, total oocyte yield, implantation rate, fertilization rate, clinical pregnancy, live births), multivariable generalized linear mixed model was used for the analysis. Increased exposure to butyl paraben was associated with a significant decrease in MII oocyte count (p = 0.007) when exposure to BP was treated as the continuous variable. Additionally, the exposure to BP in the highest quartile of exposure also decreases MII oocyte count (p = 0.02) compared to the lowest quartile. Urinary concentrations of BP were not related to total oocyte count, fertilization and implantation rate, clinical pregnancy, and live birth when the exposure variable was continuous variable or in the quartiles of exposure. Exposure to MP, EP, PP, the sum of examined parabens, and benzophenone-3 were not related to any of the examined reproductive outcomes. Exposure to butyl paraben was associated with a decrease in MII oocyte count among women attending fertility clinic rinsing concerns that exposure may have a potential adverse impact on embryological outcomes. The results emphasize the importance to reduce chemicals in the environment in order to minimize exposure. As this is the first study showing such an association, further research is needed to confirm these novel results in other populations.Graphical

Assessing the Effects of Ozonation on the Concentrations of Personal Care Products and Acute Toxicity in Sludges of Wastewater Treatment Plants.

The aim of this study was to understand the distribution of the personal care products nonylphenol (NP), triclosan (TCS), benzophenone-3 (BP-3), and caffeine in the sludges from three wastewater treatment plants (WWTP-A, -B, and -C) in southern Taiwan. The four compounds were analyzed from activated sludge and dewatered sludge samples, and then the samples were treated with pressure-assisted ozonation under different conditions and removal efficiencies. All four target compounds were detected, especially NP, which was detected in the highest concentrations in the activated sludges of WWTP-A and dewatered sludges of WWTP-C at 17.19 ± 4.10 and 2.41 ± 1.93 µg/g, respectively. TCS was dominant in dewatered sludges from WWTP-B, and the highest detected concentration was 13.29 ± 6.36 µg/g. Removals of 70% and 90% were attained under 150 psi at 40 cycles for NP and TCS, respectively, with 5 min of ozonation reaction time, a solid/water ratio of 1:20, and 2% ozone concentration. Ecological risk quotients (RQs) were calculated by the ratios of the 10-day Hyalella azteca (freshwater amphipod) LC50 to the environmental concentrations of the target compounds. High RQs were found to be >10 for NP, TCS, and BP-3 in untreated sludges, resulting in significant ecological risks to aquatic organisms when the sludges are arbitrarily disposed. However, the toxic effects on Hyalella azteca were not significantly different among ozone sludge treatments. The reason for this may be related to the formation of toxic oxidation by-products and incomplete mineralization of organic compounds. This could also be true for unknown intermediates. The relatively high detection frequencies of these emerging compounds in WWTP sludges requires further applications and treatments.

Highly selective water-compatible molecularly imprinted polymers for benzophenone-4

Molecularly imprinting technology was applied for preparing selective sorbents for benzophenone-4 (BP4), an organic UV filter used in sunscreens and cosmetics. Several imprinted polymers were prepared by bulk polymerization, using BP4 as template. Combination of stability (mechanical and chemical), selectivity and robustness of the imprinted polymers with BP4 properties resulted in a successful imprinting process (imprinting factors in range 1.05?2.60). The prepared polymers were characterised by infrared spectroscopy, elemental analysis, conductometric titrations and nitrogen physisorption at 77 K. Adsorption capacities and selectivity towards 7 other organic UV filters (benzophenone-3, benzophenone-8, homosalate, butyl methoxydibenzoylmethane, ethyl hexyl salicylate, ethyl hexyl p-dimethylamino benzoate and ethyl hexyl p-methoxycinnamate) were determined, proving high adsorption capacity and high selectivity for BP4 binding. The highest adsorption capacity was observed for 4-vinylpyridine/ethylene glycol dimethacrylate co-polymer prepared in dimethyl sulfoxide (1.108 mmol g-1). The imprinted polymer with the highest binding capacity was applied to solid phase extraction of BP4 from aqueous solutions with 98.5 % efficiency.

A novel inclusion complex of oxybenzone with C-methylresorcin[4]arene deters skin permeation.

Oxybenzone (OXB), a very widely used sunscreen ingredient has the potential to block both UVA and UVB but can penetrate through skin. Studies have revealed its presence in the blood and urine of most humans, which may lead to long-term health effects. As the confined cavities of macrocycles can alter the physical and chemical properties of encapsulated guests, in this study, we investigated the formation of host-guest complexes between C-methylresorcin[4]arene and OXB. Combined experimental (NMR spectroscopy, UV/vis absorption, and fluorescence spectroscopy) and theoretical investigation confirmed the formation of a weak host-guest complex that had a 1 : 1 stoichiometry. Furthermore, skin permeation testing revealed that complexation by C-methylresorcin[4]arene significantly reduced the skin permeation of OXB which can potentially limit the harmful effects of this organic sunscreen.

A combined experimental and theoretical study on p-sulfonatothiacalix[4]arene encapsulated sulisobenzone

Sunscreen ingredients such as sulisobenzone (SBZ) have the tendency to degrade when exposed to UV-radiation, which becomes a major problem for their further development and application in the cosmetic industry.

Prenatal exposure to phenols and benzophenones in relation to markers of male reproductive function in adulthood.

Environmental exposure during fetal life may disrupt testicular development. In humans, a limited number of studies have investigated whether these adverse effects persist into adulthood. Using data from a prospective, population-based birth cohort study, The Copenhagen Mother-Child cohort, the objective was to assess if there is an association between fetal exposure to selected phenols and benzophenones and markers of testicular function in adult men. Pregnant women were recruited in 1997-2001. Their sons were examined clinically at 18-20 years of age, with focus on adult markers of reproductive function (anogenital distance (AGD), semen quality and reproductive hormones). In total, 101 18-20-year-old men were included, whose mothers during pregnancy had a serum sample drawn and analyzed for bisphenol A (BPA) and seven other simple phenols, as well as six benzophenones. To investigate the association between chemical levels (in tertiles, T1-T3) in relation to markers of reproductive function, univariate and multiple linear regression analyses were performed. In fully adjusted analyses, increased levels of luteinizing hormone (LH) were observed with higher fetal exposure to BPA (percentage difference (95%CI)) (T2: 12% (-8%,36%) and T3: 33% (10%,62%), compared to T1) and benzophenone-3 (BP-3) (T2: 21% (-2%,49%), T3: 18% (-4%,45%)), while no clear association was seen to total testosterone (TT). Higher levels of BPA and BP-3 were associated with a lower TT/LH ratio, although only significant for BPA (p-trend=0.01). No associations were seen to AGD or markers of semen quality. In conclusion, high exposure to BPA and BP-3 was associated with a compensated reduced Leydig cell function but no other changes in markers of reproductive health. As maternal levels of BPA and BP-3 were not correlated, separate effects may be at play. Larger studies on long-term reproductive consequences of prenatal exposures are warranted to validate our findings.