Joint Effects of Multiple UV Filters on Zebrafish Embryo Development.

The widespread use of UV filters has resulted in significant amounts of these chemicals appearing not only in the environment but also in organisms. This study first assessed the levels of nine UV filters in waters along the coast of Shenzhen, China, in tapwater, and in a nearby reservoir. UV filters were found to be high, in both winter and summer at most locations. Then, using zebrafish as a model, the influence of a UV filter mixture after dietary and aqueous exposure was assessed. After exposing artemia to three dominant UV filters at two levels and then feeding these artemia to zebrafish adults, concentrations in both were up to 4 times higher when exposed to the mixtures than when exposed to only a single UV filter. A short-term 25-day dietary exposure to the zebrafish adults did not appear to significantly influence early life stage development of the second generation; however, relatively long exposure over 47 days had significant adverse effects on embryo development. Aqueous exposure of fish embryos to mixtures of the three UV filters demonstrated a general trend of decreased heart/hatching rate as doses increased, coupled with significant changes in activities of catalase and malate dehydrogenase.

Hybrid radical coupling during MnO2-mediated transformation of a mixture of organic UV filters: Chemistry and toxicity assessment.

Manganese oxide (MnO2) is one of the most abundant metal oxides, and it is renowned for its ability to degrade various phenolic micropollutants. However, under MnO2-mediated transformation, BP-3 transforms into 12 different radical-coupled transformation products (TPs) out of 15 identified TPs. These radical-coupled TPs are reported with adverse environmental impacts. This study explored the effects of MnO2 on organic UV filter mixtures and different water constituents (i.e., bicarbonate ion (HCO3-), humic acid (HA) and halide ions) in terms of degradation efficiency and transformation chemistry. When a mixture of benzophenone-3 (BP-3) and avobenzone (AVO) underwent transformation by MnO2, hybrid radical-coupled TPs derived from both organic UV filters were generated. These hybrid radical-coupled TPs were evaluated by an in silico prediction tool and Vibrio fischeri bioluminescence inhibition assay (VFBIA). Results showed that these TPs were potentially toxic to aquatic organisms, even more so than their parent compounds. The higher the concentration of HCO3-, HA, chloride ion (Cl-) and bromide ion (Br-), the greater the reduction in the efficiencies of degrading BP-3 and AVO. Contrastingly, in the presence of iodide ion (I-), degradation efficiencies of BP-3 and AVO were enhanced; however, iodinated TPs and iodinated radical-coupled TPs were formed, with questionable toxicity. This study has revealed the environmental risks of hybrid radical-coupled TPs, iodinated TPs and iodinated radical-coupled TPs when the organic UV filters BP-3 and AVO are transformed by MnO2.

Fate of quaternary ammonium compounds upon the UV/monochloramine process: Kinetics, transformation pathways and the formation of N-nitroso-N-methyl-N-alkylamines.

Quaternary ammonium compounds (QACs) are widely detected in the aquatic environment due to their extensive use in a wide array of antibacterial products during the pandemic. In the current study, UV/monochloramine (UV/NH2Cl) was used to degrade three typical QACs, namely benzalkonium compounds (BACs), dialkyl dimethyl ammonium compounds (DADMACs), and alkyl trimethyl ammonium compounds (ATMACs). This process achieved high efficiency in removing BACs from water samples. The transformation products of QACs treated with UV/NH2Cl were identified and characterized using a high-resolution mass spectrometer, and transformation pathways were proposed. The formation of N-nitroso-N-methyl-N-alkylamines (NMAs) and N-nitrosodimethylamine (NDMA) were observed during QAC degradation. The molar formation yield of NDMA from C12-BAC was 0.04 %, while yields of NMAs reached 1.05 %. The ecotoxicity of NMAs derived from QACs was predicted using ECOSAR software. The increased toxicity could be attributed to the formation of NMAs with longer alkyl chains; these NMAs, exhibited a one order of magnitude increase in toxicity compared to their parent QACs. This study provides evidence that QACs are the specific and significant precursors of NMAs. Greater attention should be given to NMA formation and its potential threat to the ecosystem, including humans.

Hazardous radical-coupled transformation products of benzophenone-3 formed during manganese dioxide treatment.

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.

The quest for metabolic biomarkers of agrochemicals exposure via in vitro studies and suspect screening.

Numerous agrochemicals, including pesticides and herbicides, are applied in modern agriculture, resulting in concerns for the ecosystem and human safety as humans are easily exposed to these compounds. Many agrochemicals, and their transformation products or metabolites, have shown toxicity in in vitro and in vivo studies. However, given the rapid development of novel agrochemicals, for many there is no information about their effects nor about metabolic transformations when ingested by humans. Tracing biomarkers may be the best method for assessing the impacts of agrochemicals. A combination of in vitro metabolism study and suspect screening of human samples (e.g., urine, blood) can be utilized to efficiently find biomarkers for agrochemical exposure. In the work reported here, we determined the in vitro metabolic profiling of six prioritized pesticides and synergists, namely boscalid, carbendazim, piperonyl butoxide, spiroxamine, dimethomorph and fludioxonil, in human liver microsomes. 17 major metabolites were structurally elucidated by high resolution mass spectrometry (HRMS). Major metabolic transformation processes (e.g., hydroxylation, demethylation and oxidation) were proposed for each pesticide. Individual in silico toxicity assessments showed that some metabolites had the same or even enhanced toxicity compared to parent compounds. Information about these metabolites obtained from HRMS was used for suspect screening in human activities related samples. Carbendazim and a metabolite of fludioxonil were identified in wastewater and laboratory urine samples, respectively. Our findings provide concrete evidence for the use of in vitro metabolites as biomarkers in biomonitoring studies of potential exposure to toxic chemicals.

Chlorination of bisphenols in water: Understanding the kinetics and formation mechanism of 2-butene-1,4-dial and analogues.

While it is widely accepted that 2-butene-1,4-dial (BDA) is a toxic metabolite with genotoxic and carcinogenic properties, little is known about BDA and its analogues (BDAs) formation during water disinfection. In this study, the effects of different chlorination conditions on the formation of BDAs from bisphenol and its analogues (BPs analogues) were evaluated. A transformation pathway for the formation of BDAs upon chlorination of BPs analogues is proposed. The time profile of the transformation of BPs analogues into BDAs reveals that the generation of dichlorohydroquinone, dichloro-hydroxybenzenesulfonic acid and 2,4,6-trichlorophenol, are significantly associated with the formation of BDAs in the disinfected water. Owing to the different bridging groups contributing to the electrophilicity of BPs analogues in varying degrees, the stronger the electrophilicity of BPs analogues the more BDAs are formed. In addition, the type of BDAs produced is also affected. Four types of BDAs were detected in this study, one of which was newly identified. This study confirms that BPs analogues are an important source of BDAs and provides more insights into the formation of BDAs during chlorination. Greater attention should be given to the formation of BDAs in chlorinated water and their potential threat to humans and the ecosystem.

Co-exposure to organic UV filters and phthalates and their associations with oxidative stress levels in children: A prospective follow-up study in China.

Children are highly vulnerable to environmental pollutants, especially endocrine-disrupting chemicals (EDCs). Previous research has linked both organic UV filters and phthalates exposure to adiposity and pubertal development in children. Nevertheless, the individual and collective effects of these chemicals on this population remain poorly understood. In this study, twelve organic UV filters and metabolites, six phthalate metabolites and two oxidative stress biomarkers were analyzed in a prospective follow-up study in Shanghai, China after a baseline study conducted 1.5 years earlier. Results revealed a positive association between exposure to individual organic UV filters or their mixture and levels of 8-OHdG (ß ranging from 0.242 to 0.588, P < 0.05), a marker of oxidative DNA damage. BP-3 and OD-PABA made a greater contribution to oxidative DNA damage than other UV filters. Levels of 8-OHdG were also positively correlated with single phthalate metabolites and their mixture, with MnBP and MMP contributing the most. Stratified analysis found that these associations were mainly observed in girls. Our mixture analysis revealed cumulative risks of oxidative DNA damage when there was co-exposure to these two kinds of EDCs. These results underscore the importance of considering the risks associated with organic UV filters and the necessity of evaluating the effects of all these pollutants, both individually and in mixtures.

Degradation of acesulfame in UV/monochloramine process: Kinetics, transformation pathways and toxicity assessment.

UV/monochloramine (UV/NH2Cl) is an emerging advanced oxidation process that can generate various reactive species like reactive chlorine species (RCS) and hydroxyl radicals for micropollutant removal. This study investigated the potential toxicity of transformation products resulting from UV/NH2Cl treatment of acesulfame (ACE), as an example of micropollutant, found in worldwide aquatic environment. Compared with UV photolysis and chloramination, the UV/NH2Cl process more effectively degraded ACE. The transformation products of ACE treated with the UV/NH2Cl process were identified and characterized with high resolution mass spectrometry. The formation of chlorinated-TPs indicated the role of RCS in UV/NH2Cl transformation even though UV photolysis was predominantly responsible for the ACE degradation. The Vibrio fischeri bioluminescence inhibition assay revealed a higher toxicity of TPs derived from UV/NH2Cl than from UV photolysis. The increased toxicity could be attributed to most of the generated chlorinated-TPs (Cl-TPs), in particular those halo-alcohols. The ECOSAR program predicts that halo-alcohol TPs are more toxic than their non-chlorinated analogues and other Cl-TPs. This study provides insight into the important role of reactive species in the micropollutants' transformation of UV/NH2Cl process. It further provides information relevant to the potential risk when applying the process for micropollutant removal in water treatment.

Risks of organic UV filters: a review of environmental and human health concern studies.

Organic UV filters are compounds that absorb UV irradiation by their highly conjugated structure. With the developing consciousness over the last century of the skin damage UV radiation can cause, the demand for organic UV filters has risen, for use not only in sunscreens, but also in other personal care products. The massive production and usage of these organic UV filters has resulted in extensive release into the aquatic environment, and thereby making an important group of emerging contaminants. Considering the widespread occurrence of organic UV filters in not only ambient water, but also sediment, soil and even indoor dust, their threats towards the health of living organisms have been a subject of active investigation. In this review article, we present an overall review of existing knowledge on the risks of organic UV filters from the aspects of both environmental and human health impacts. As for the environment, some organic UV filters are proven to bioaccumulate in various kinds of aquatic organisms, and further to have adverse effects on different kinds of animal models. Toxicological studies including in vivo and in vitro studies are important and effective means to ascertain the effects and mechanisms of organic UV filters on both the ecosystem and humans. Subsequent concerns arise that these compounds will affect human health in the long term. This review concludes by suggesting future lines of research based on the remaining knowledge gaps.

Comparative physicochemical properties and toxicity of organic UV filters and their photocatalytic transformation products.

Transformation products (TPs) of micropollutants contaminating our water resources have become an emerging issue due to the potential threats they pose to environmental and human health. This study investigated the transformation chemistry, toxicity, physicochemical properties and environmental behavior resulting from photocatalytic transformation of organic UV filters as model micropollutants. 3-Benzylidene camphor (3-BC), 4-hydroxybenzophenone (4-HB) and octocrylene (OC) were effectively degraded by UV-A/TiO2 treatment, with TPs identified and characterized with high resolution mass spectrometry. Nitrated-TPs were observed to be formed in the presence of nitrite and nitrate for 3-BC and 4-HB, suggesting that the transformation process could be altered by components in the water matrix. Vibrio fischeri bioluminescence inhibition assay revealed an increase in toxicity of TPs derived from photocatalytic treatment, with quantitative structure-activity relationship model (ECOSAR) predicted an enhanced toxicity of individual TPs' after transformation. Assessment of physicochemical properties and environmental behavior suggested that TPs as compared to parent organic UV filters, may represent even greater hazards due to their increased water solubility, persistence and mobility - in addition to retaining the parent organic UV filter's toxicity. The results provide important information relevant to the potential risks for the selected organic UV filters, and their corresponding transformation products.

Acesulfame aerobic biodegradation by enriched consortia and Chelatococcus spp.: Kinetics, transformation products, and genomic characterization.

The artificial sweetener Acesulfame (ACE) has been frequently detected in wastewater treatment plants (WWTPs) and is regarded as an emerging pollutant due to its low biodegradability. However, recent observations of ACE biodegradation in WWTPs have stimulated interest in the ACE-degrading bacteria and mineralization pathways. In this study, next-generation sequencing methods, Illumina and Nanopore sequencing, were combined to explore the ACE-degrading communities enriched from the activated sludge of six municipal wastewater treatment plants. Metagenomic investigations indicated that all enrichments were similarly dominated by the phyla Proteobacteria and Planctomycetes. Notably, at the species level, four metagenome-assembled genomes (MAGs) were shared by six enriched communities with considerable abundances, indicating that they may be responsible for ACE biodegradation in the enrichments. Besides, two ACE-degrading pure strains, affiliated to the genus Chelatococcus, were isolated from the enrichment. The genomic analysis showed that these two isolates were the new species that were genetically distinct from their relatives. Two type strains, Chelatococcus asaccharovorans DSM 6462 and Chelatococcus composti DSM 101465, could not degrade ACE, implying that the ACE-degrading capability was not shared among the different species in the genus Chelatococcus. The results of the degradation experiment showed that the two isolates could use ACE as the sole carbon source and mineralize ~90% of the total organic carbon. Three biotransformation products (TP96, TP180B, and TP182B) were demonstrated by UPLC-QTOF-MS. The results of this study provide valuable insights into ACE biodegradation and its biotransformation products.

Effects of Weathering on the Sorption Behavior and Toxicity of Polystyrene Microplastics in Multi-solute Systems.

Recent studies have demonstrated that weathering modifies the physicochemical properties and sorption behavior of microplastics (MPs). However, little is known about the effects of such weathering on the simultaneous sorption by MPs of different organic pollutants in multi-solute systems. In this study, the role of cosolute properties in the formation of solute multilayers with a hydrophobic primary solute (4-MBC) on pristine and various weathered polystyrene MPs (PSMPs) was examined. Three weathered PSMPs were studied namely, UV-irradiated PS (UV-PS), microbially degraded PS (MD-NPS), and UV-irradiated PS with subsequent microbial degradation (MD-UV-PS). The weathered PSMPs generally exhibited higher degree of oxygenated functionalities with less surface hydrophobicity than pristine particles. Our findings showed that the formation of solute multilayers with hydrophobic cosolutes was drastically suppressed in UV-PS due to more severe competition at hydrophobic sorption sites. Nevertheless, hydrophilic cosolutes contributed to solute multilayer formation with 4-MBC on PSMPs after UV irradiation, probably due to the stronger sorption of hydrophilic compounds to the oxidized surfaces of these particles via enhanced H-bonding. Strikingly, the sorption of 4-MBC by MD-UV-PS was notably enhanced when hydrophobic cosolutes were present. The observed synergistic sorption indicates that adhered biofilms and/or organic matter on MD-UV-PS could sorb the hydrophobic cosolute molecules, and eventually promote sorption of 4-MBC. Our further toxicity tests revealed that such solute multilayers formed on PSMPs inhibited microalgal growth. These results suggest that the fate and biological effects of MP-mediated chemical exposure could be strongly affected by weathering processes and coexistence of multiple organic contaminants in natural environments.

Organic UV filter exposure and pubertal development: A prospective follow-up study of urban Chinese adolescents.

BACKGROUND: UV filters, widely used in personal care and industrial products, are being found in the environment and, in humans where with limited understanding on their potential health effects, especially during puberty. OBJECTIVES: To examine the association between UV filter exposure and pubertal development in a prospective follow-up study. METHODS: This study included 521 elementary and high school students from a suburban area of Shanghai. The initial study was done in October to November 2011; the follow-up study in April to May 2013. Twelve urinary organic UV filters were quantified, and the pubertal development was assessed at each study period by trained physicians using Tanner staging. We used (ordered) logistic regression model and multilevel mixed-effect (ordered) logistic regression model to assess cross-sectional and longitudinal effects between urinary concentration of five major UV filters and pubertal development of stages, onset and pace. RESULTS: Ethylhexyl methoxycinnamate (EHMC) and its metabolite 4'-methoxyacetophenone (4'-MAP), two benzophenone derivatives (BP-2, BP-3) and Ethylhexyl dimethyl PABA (OD-PABA) were the most extensively detected UV filters in urine with geometric means (95% CI) in 2010 and 2012 as 1.77 (1.599, 1.956) and 2.28 (1.985, 2.622) ng/mL for EHMC; 4.55 (4.219, 4.907) and 5.26 (4.783, 5.775) ng/mL for 4'-MAP; 4.38 (4.011, 4.774) and 5.74 (5.023, 6.562) ng/mL for BP-2; 0.83 (0.760, 0.903) and 1.09 (0.967, 1.220) ng/mL for BP-3; 5.37 (4.949, 5.820) and 5.80 (5.193, 6.486) pg/mL for OD-PABA. Significant trend P-values (P < 0.05) include: EHMC and its metabolite were negatively correlated with stages of testicular volume and genital development; BP-3 was also negatively correlated with stages of testicular volume in boys, while OD-PABA positively correlated with stages of pubic hair and breast development in girls. Also, EHMC was associated with later pubertal onset of pubic hair and testicular volumes in boys, while OD-PABA correlated with earlier pubertal onset of breast development in girls. OD-PABA also significantly speeded up the progression of pubic hair and breast development in girls. DISCUSSION: UV filters were extensively detected. Exposure to EHMC and BP-3 was significantly associated with later pubertal development in boys, and OD-PABA was associated with earlier pubertal development in girls. It demonstrates that the UV filters so widely used in personal care products and widely detected in environments are finding their way back into people where they are distorting endocrine function of adolescents.

Redox mediators and irradiation improve fenton degradation of acesulfame.

Widely recognized as a promising approach to degrading recalcitrant pollutants, Advanced Oxidation Processes (AOPs) have drawn much attention for their effectiveness and efficiency. Among all the AOPs, the Fenton system has been widely applied for oxidation and mineralization of micropollutants due to its ease of implementation and high catalytic efficiency. However, the necessity of preceding acidification, together with rapid consumption and slow regeneration of Fe(II) resulting in deterioration of reactivity, has reduced its competitiveness as a practical option for water treatment. Acknowledging the above drawbacks, this study investigates the potential viable option to enhance the Fenton system. Acesulfame was chosen as the model compound due to its ubiquitous occurrence and persistence in the environment. UV-assisted photo-Fenton treatment was found to remove the parent compound effectively; the transformation profile of acesulfame was identified and elucidated with the ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Prolonged UV photo-Fenton treatment was effective for mineralization of the majority of the transformation products, without increasing the overall toxicity as indicated by Vibrio fischeri bioluminescence assay. The positive effects of the addition of redox mediators to Fenton systems at neutral pH were confirmed in this study. The results could be the basis for further development of homogeneous catalytic degradation techniques for the oxidation of environmental contaminants at circumneutral pHs to neutral pHs.

Fate of UV filter Ethylhexyl methoxycinnamate in rat model and human urine: Metabolism, exposure and demographic associations.

Ethylhexyl methoxycinnamate (EHMC) is one of the most frequently used UV filters in sunscreens and other cosmetic products. Its ubiquitous presence in various environmental matrices and its endocrine disrupting properties have been widely reported. However, we know little about the effect of EHMC exposure on humans, mainly due to its fast metabolism. In this study, urine and plasma of EHMC-dosed rats were analysed to identify its major metabolites. Five metabolites were found, with four firstly reported. Two metabolites were putatively identified as 4-methoxycinnamic acid (4-MCA) and 4'-methoxyacetophenone (4'-MAP). Quantitative results revealed that their excretion concentrations were much higher than the parent compound. Because of these high concentrations, for the human biomonitoring study, EHMC and these two metabolites were detected simultaneously in urine samples from Chinese children and adolescents. The results indicated wide exposure to EHMC, 4-MCA and 4'-MAP. The correlation between urinary concentration of EHMC and 4-MCA as well as 4-MCA and 4'-MAP provided important clues as to the sources and metabolic pathways among these three compounds. Several demographic factors were also assessed with the exposure level. As the first human exposure study of EHMC in a Chinese population, this report would help to establish an exposure database facilitating health risk assessment of EHMC.

Environmental behavior of 12 UV filters and photocatalytic profile of ethyl-4-aminobenzoate.

Ethyl-4-aminobenzoate (Et-PABA) is currently used as a substitute for 4-aminobenzoate (PABA) in sunscreens and anesthetic ointments. Despite its widespread use and hydrophilicity, Et-PABA has never been found in environmental waters. This study, probed the occurrence of Et-PABA in both seawater and drinking water sources in Hong Kong, and evaluated its transformation products (TPs) and environmental fate via cumulative potency and photocatalytic profile analyses. Another 11 UV filters used in skin-care products were also studied. Et-PABA was not detected in any water sample. Four other UV filters were dominant at ng/L level in both seawater and drinking water sources. UHPLC-QTOF-MS was used to elucidate the structure of TPs. With high resolution accurate mass data and fragment rationalization, 11 Et-PABA TPs were characterized, including seven intermediates firstly proposed as TPs; two compounds were reported for the first time. It is proposed that photocatalysis induces transformation pathways of (de)hydroxylation, demethylation and molecular rearrangement. Luminescent bacteria tests showed decreasing toxicity with increasing irradiation of Et-PABA, suggesting that irradiation TPs are less toxic than the parent compound. Transformation of Et-PABA appears to explain why Et-PABA has not been detected in the natural environment.

Transformation of acesulfame in chlorination: Kinetics study, identification of byproducts, and toxicity assessment.

Acesulfame (ACE) is one of the most commonly used artificial sweeteners. Because it is not metabolized in the human gut, it reaches the aquatic environment unchanged. In the present study, the reactivity of ACE in free chlorine-containing water was investigated for the first time. The degradation of ACE was found to follow pseudo-first-order kinetics. The first-order rate increased with decreasing pH from 9.4 to 4.8 with estimated half-lives from 693 min to 2 min. Structural elucidation of the detected transformation products (TPs) was performed by ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Integration of MS/MS fragments, isotopic pattern and exact mass allowed the characterization of up to 5 different TPs in the ultrapure water extracts analyzed, including two proposed new chlorinated compounds reported for the first time. Unexpectedly, several known and regulated disinfection by-products (DBPs) were present in the ACE chlorinated solution. In addition, two of the six DBPs are proposed as N-DBPs. Time-course profiles of ACE and the identified by-products in tap water and wastewater samples were followed in order to simulate the actual disinfection process. Tap water did not significantly affect degradation, but wastewater did; it reacted with the ACE to produce several brominated-DBPs. A preliminary assessment of chlorinated mixtures by luminescence inhibition of Vibrio fischeri showed that these by-products were up to 1.8-fold more toxic than the parent compound. The generation of these DBPs, both regulated and not, representing enhanced toxicity, make chlorine disinfection a controversial treatment for ACE. Further efforts are urgently needed to both assess the consequences of current water treatment processes on ACE and to develop new processes that will safely treat ACE. Human health and the health of our aquatic ecosystems are at stake.