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.

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.

Transformations of organic micropollutants undergoing permanganate/bisulfite treatment: Kinetics, pathways and toxicity.

Permanganate/bisulfite (PM/BS) is a relatively new advanced oxidation process that can degrade organic micropollutants at extraordinary high rates. In this study, the degradability of PM/BS process towards different representative types of compounds was studied by investigating the kinetics, reaction site specificity and transformation chemistry. Acesulfame (ACE) and carbamazepine (CBZ) were two typical compounds containing olefinic moieties. Sucralose (SUC) was selected as a reference compound, and it is without aromatic and olefinic moieties. The kinetics results indicated that ACE and CBZ were effectively degraded while SUC was not. Preferred reaction sites of Mn3+ species was elucidated by identification of the ACE-transformation products (TPs) and CBZ-TPs with UHPLC-QTOF-MS. Seventeen ACE-TPs including two new compounds and eleven CBZ-TPs produced during the PM/BS process were identified and characterized. Transformation pathways revealed that cleavage of olefinic double bonds was the main reaction mechanism. Chemical structures containing electron-donating groups preferentially reacted with electrophilic Mn3+ species during the process. In addition, transformation products of ACE and CBZ during PM/BS process did not induce higher toxicity. This study provides a preliminary interpretation on the selectivity of PM/BS process according to the micropollutants' chemical structures, which hope to shed light on the future development of PM/BS treatment.

Removing acesulfame with the peroxone process: Transformation products, pathways and toxicity.

Emerging contaminants (ECs) are receiving considerable attention because of their widespread occurrence, persistence and potential threat to the environment, wildlife and humans. Acesulfame (ACE), an extensively used artificial sweetener, is the most worrisome example of ECs. The photolysis/photocatalysis, chlorination and/or permanganate oxidation of ACE produces transformation products (TPs) that are more persistent and toxic than precursors. Thus, an alternative treatment method to treat ACE is required; oxidation by the peroxone process could be that method and was systematically investigated, as reported here. During the peroxone process, ACE degradation followed pseudo-first-order kinetics, with a rate that was significantly higher than after conventional ozonation. The hydroxyl radical was the major reactive species. Amount of hydrogen peroxide (H2O2) used, pH and type of water matrix showed significant influence on ACE degradation. Fifteen TPs in ultrapure water extracts, including four newly reported compounds, were identified and characterized by high resolution mass spectrometry (HR-MS) based on accurate mass measurements and MS/MS fragmentation. The reduced toxicity compared to other reported treatments of ACE was likely due to different transformation pathways and TPs generated. The peroxone process therefore appears to be one viable choice for safe removal of ACE.

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.

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.