Degradation of organic UV filters in the water environment: A concise review on the mechanism, toxicity, and technologies.

Organic ultraviolet filters (OUVFs) have been used globally for the past 20 years. Given that OUVFs can be quickly released from sunscreens applied on human skins, they have been frequently detected in aquatic environments and organisms. Some byproducts of OUVFs might be more recalcitrant and toxic than their parent compounds. To further assess the toxicity and potential risk of OUVFs' byproducts, it is necessary to determine the fate of OUVFs and identify their transformation products. This review summarizes and analyzes pertinent literature and reports in the field of OUVFs research. These published research works majorly focus on the degradation mechanisms of OUVFs in aquatic environments, their intermediates/byproducts, and chlorination reaction. Photodegradation (direct photolysis, self-sensitive photolysis and indirect photolysis) and biodegradation are the main transformation pathways of OUVFs through natural degradation. To remove residual OUVFs' pollutants from aqueous environments, novel physicochemical and biological approaches have been developed in recent years. Advanced oxidation, ultrasound, and bio-based technologies have been proven to eliminate OUVFs from wastewaters. In addition, the disinfection mechanism and the byproducts (DBPs) of various OUVFs in swimming pools are discussed in this review. Besides, knowledge gaps and future research directions in this field of study are also mentioned.

Occurrence, behavior and fate of liquid crystal monomers in municipal wastewater.

Liquid crystal monomers (LCMs), the essential substances used in the display screen of electronic devices, have been proposed as a class of emerging chemicals of concern. Despite their detection in various environmental matrices, little is known about the presence of LCMs in municipal sewage systems. This study aimed to investigate the occurrence, distribution, and fate of 64 LCMs released into the aqueous environment from a municipal wastewater treatment plant (WWTP) in Hong Kong, China. In total 14 LCMs were detected in WWTP samples. Specifically, the Σ14LCMs concentrations in crude influent, final effluent, and final sludge were found to be 16.8 ± 0.3 ng/L, 2.71 ± 0.05 ng/L, and 19.2 ± 1.0 ng/g dry weight, respectively. Among them, 10 fluorinated LCMs (F-LCMs) were determined to be present at concentrations of 8.90 ± 0.10 ng/L, 1.69 ± 0.05 ng/L, and 9.94 ± 1.00 ng/g dry weight, respectively. The predominant non-fluorinated LCMs (NF-LCMs) detected in all samples were 3OCB and EPhEMOB, while 2OdF3B was the dominant F-LCM. The overall removal rate of total LCMs was 83.8 ± 0.3 %, with 25.4 ± 4.8 % being removed by biodegradation and UV treatment. Compared to NF-LCMs, F-LCMs were more resistant to biodegradation. Despite the significant removal of LCMs through WWTP, the remaining LCMs in final effluent could result in an annual emission of 3.04 kg of total LCMs from the population of Hong Kong. This study provides the first evidence of LCMs contamination in municipal wastewater, possibly arising from routine electronic devices usage. Further investigation is needed to elucidate the potential impact of LCMs emission via WWTP effluent on the aquatic receiving ecosystem.

Identification of Transformation Products of Organic UV Filters by Photooxidation and Their Differential Estrogenicity Assessment.

Organic ultraviolet filters (OUVFs) are extensively released into aquatic environments, where they undergo complex phototransformation. However, there is little knowledge regarding their transformation products (TPs) and associated endocrine disruption potentials. In the present study, we characterized the chemical and toxicological profiles of TPs for two common OUVFs, oxybenzone (BP3) and ethylhexyl methoxycinnamate (EHMC), by photooxidation under environmentally relevant conditions. It is hypothesized that TPs of the tested OUVFs will show varied estrogenicity at different reaction times. High-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) identified 17 TPs of 7 m/z for BP-3 and 13 TPs of 8 m/z for EHMC at confidence levels ≤2. Five novel TPs of 2 m/z were reported for the first time with structure-diagnostic MS/MS spectra. Estrogenicity assessment using the MCF-7-luc cell line showed discrepant estrogenic activities exhibited by OUVF-TPs over time. Specifically, BP3-TPs exhibited significantly greater estrogenicity than the parent at several reaction times, whereas EHMC-TPs displayed fluctuating estrogenicity with a declining trend. Correlation analysis coupled with molecular docking simulations further suggested several TPs of BP3 as potential endocrine disruptive compounds. These findings underscore the necessity of considering mixtures during chemical testing and risk assessment and highlight the potentially greater risks associated with post-transformation cocktails.

Liquid crystal monomers in ventilation and air conditioning dust: Indoor characteristics, sources analysis and toxicity assessment.

Indoor dust contaminated with liquid crystal monomers (LCMs) released from various commercial liquid crystal display (LCD) screens may pose environmental health risks to humans. This study aimed to investigate the occurrence of 64 LCMs in ventilation and air conditioning filters (VACF) dust, characterize their composition profiles, potential sources, and associations with indoor characteristics, and assess their in vitro toxicity using the human lung bronchial epithelial cells (BEAS-2B). A total of 31 LCMs with concentrations (ΣLCMs) ranging from 43.7 ng/g to 448 ng/g were detected in the collected VACF dust. Additional analysis revealed the potential interactions between indoor environmental conditions and human exposure risks associated with the detected LCMs in VACF dust. The service area and working time of the ventilation and air conditioning system, and the number of indoor LCD screens were positively correlated with the fluorinated ΣLCMs in VACF dust (r = 0.355 âˆ¼ 0.511, p < 0.05), while the associations with the non-fluorinated ΣLCMs were not found (p > 0.05), suggesting different environmental behavior and fates of fluorinated and non-fluorinated LCMs in the indoor environment. Four main indoor sources of LCMs (i.e., computer (37.1%), television (28.3%), Brand A smartphone (21.2%) and Brand S smartphone (13.4%)) were identified by positive matrix factorization-multiple linear regression (PMF-MLR). Exposure to 14 relatively frequently detected LCMs, individually and in the mixture, induced significant oxidative stress in BEAS-2B cells. Among them, non-fluorinated LCMs, specifically 3cH2B and MeP3bcH, caused dominant decreased cell viability. This study provides new insights into the indoor LCMs pollution and the associated potential health risks due to the daily use of electronic devices.

New Perspective to Understand and Prioritize the Ecological Impacts of Organophosphate Esters and Transformation Products in Urban Stormwater and Sewage Effluents.

Due to their prevalence in urban contaminated water, the driving factors of organophosphate esters (OPEs) need to be well examined, and their related ecological impacts should include that of their transformation products (TPs). Additionally, a robust framework needs to be developed to integrate multiple variables related to ecological impacts for improving the ecological health assessment. Therefore, OPEs and TPs in urban stormwater and wastewater in Hong Kong were analyzed to fill these gaps. The results revealed that the total concentrations of OPEs in stormwater were positively correlated with the area of transportation land. Individual TP concentrations and the mass ratios of individual TPs/OPEs were somewhat higher in sewage effluents than that in stormwater. OPEs generally showed relatively higher risk quotients than TPs; however, the total risk quotients increased by approximately 38% when TPs were factored in. Moreover, the molecular docking results suggested that the investigated TPs might cause similar endocrine disruption in marine organisms as their parent OPEs. This study employed the Toxicological-Priority-Index scheme to successfully integrate the ecological risks and endocrine-disrupting effects to refine the ecological health assessment of the exposure to OPEs and their TPs, which can better inform the authority on the prioritization for regulating these contaminants of emerging concern in urban built environments.

Identification of key features relating to the coexistence mechanisms of trace elements and per- and polyfluoroalkyl substances (PFASs) in marine mammals.

Organic and inorganic substances coexist in the livers of marine mammals and may correlate with one another; however, their coexistence mechanisms and relevant key features remain largely unknown. In this study, temporal variations (2011-2021) in the concentrations of nine trace elements and 19 per- and polyfluoroalkyl substances (PFASs) in the livers of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) were investigated. Interannual Cd in dolphins increased significantly whereas Pb concentrations decreased over the past decade (p < 0.05). Interannual levels of seven and four PFASs in dolphins and porpoises decreased significantly with time (p < 0.05). By further extending the timescale to 1993-2021, the sensitivity of trace elements to annual change further increased, whereas the sensitivity of PFASs remained relatively stable. Cu levels, similar to the majority of PFASs, were negatively correlated with the body length of the studied cetaceans, which led to positive correlations of Cu with six long-chain perfluoroalkyl carboxylic acids, perfluorodecane sulfonic acid, and perfluoroethylcyclohexane sulfonic acid. The concentrations of trace elements in the cetacean liver were closely correlated with cetacean sex, species, and body length, whereas PFAS concentration was responsive to time-related features such as stranded season and year. By further employing a machine learning method, we demonstrated that body length and a time-related factor (year) played a crucial role in predicting the concentrations of certain trace elements and PFASs, respectively, particularly Cu and perfluoroheptanoic acid.

Release Behavior of Liquid Crystal Monomers from Waste Smartphone Screens: Occurrence, Distribution, and Mechanistic Modeling.

Liquid crystal display (LCD) screens can release many organic pollutants into the indoor environment, including liquid crystal monomers (LCMs), which have been proposed as a novel class of emerging pollutants. Knowing the release pathways and mechanisms of LCMs from various components of LCD screens is important to accurately assess the LCM release and reveal their environmental transport behavior and fate in the ambient environment. A total of 47, 43, and 33 out of 64 target LCMs were detected in three disassembled parts of waste smartphone screens, including the LCM layer (LL), light guide plate (LGP), and screen protector (SP), respectively. Correlation analysis confirmed LL was the source of LCMs detected in LGP and SP. The emission factors of LCMs from waste screen, SP, and LGP parts were estimated as 2.38 × 10-3, 1.36 × 10-3, and 1.02 × 10-3, respectively. A mechanism model was developed to describe the release behaviors of LCMs from waste screens, where three characteristics parameters of released LCMs, including average mass proportion (AP), predicted subcooled vapor pressures (PL), and octanol-air partitioning coefficients (Koa), involving coexistence of absorption and adsorption mechanisms, could control the diffusion-partitioning. The released LCMs in LGP could reach diffusion-partition equilibrium more quickly than those in SP, indicating that LCM release could be mainly governed through SP diffusions.

Removing emerging e-waste pollutant DTFPB by synchronized oxidation-adsorption Fenton technology.

Liquid crystal monomers (LCMs), an emerging group of organic pollutants related to electronic waste, have been frequently detected from various environmental matrices, including landfill leachate. The persistence of LCMs requires robust technology for remediation. The objectives of this study were to evaluate the feasibility, performance and mechanism of the remediation of a typical LCM 4-[difluoro(3,4,5-trifluorophenoxy)methyl]- 3,5-difluoro-4'-propylbiphenyl (DTFPB) via synchronized oxidation-adsorption (SOA) Fenton technology and verify its application in DTFPB-contaminated leachate. The SOA Fenton system could effectively degrade 93.5% of DTFPB and 5.6% of its total organic carbon (TOCDTFPB) by hydroxyl radical oxidation (molar ratio of Fe2+ to H2O2 of 1/4 and pH 2.5-3.0) following a pseudo-first-order model under 0.378 h-1. Additionally, synchronized adsorption of DTFPB and its degradation intermediates by in situ resultant ferric particles via hydrophobic interaction, complexation, and coprecipitation contributed to almost 100% of DTFPB and 33.4% of TOCDTFPB removal. Three possible degradation pathways involving eight products were proposed, and hydrophobic interactions might drive the adsorption process. It was first confirmed that the SOA Fenton system exhibited good performance in eliminating DTFPB and byproducts from landfill leachate. This study provides new insights into the potential of the Fenton process for the treatment of emerging LCMs contamination in wastewater.

Development of a fully automatic separation system coupled with online ICP-MS for measuring rare earth elements in seawater.

Rare earth elements (REEs) are useful geological indicators of marine geochemistry. However, extremely low concentrations (sub-ng L-1) and high-salt matrices result in inefficient measurements. A fully automatic separation system (ELSPE-2 Precon) is used in the online determination of ultra-trace REEs in seawater using inductively coupled plasma mass spectrometry. This system mainly comprises three sections: (i) an auto-sampler (eas-2A) with 120 positions; (ii) a poly(styrene-divinylbenzene) resin column (Prin-Cen Col007) with iminodiacetic and ethylenediaminetriacetic acid functional groups to eliminate the high-salt matrix (e.g., Na, Ca, K, Mg, Al, Ba, Fe, Sr, P, and S) and preserve the target REEs; and (iii) a Trp002 cleanup column for the reduction of the reagent and procedural blank values. The detection limits (3σ) were in the range 0.002 (Dy)-0.097 ng L-1 (La), and the long-term reproducibility (8 h) was between 80% and 120% for all REEs in a 3.5% NaCl matrix solution. The accuracy of this method was verified using a seawater reference material (NASS-6), and the measured REE concentrations were consistent with those previously reported. The proposed online system was used to investigate coastal water samples with varying salinities from the Pearl River Estuary (Guangdong, China). Variations in the REE distribution patterns of different layers of seawater were observed, which could be due to the mixing of potentially light rare earth element-enriched bottom seawater. Moreover, a positive Gd anomaly in river water and seawater might be attributed to anthropogenic pollution from hospitals and the pharmaceutical industry.

A systematic study of microplastic occurrence in urban water networks of a metropolis.

The release of microplastics from sewage treatment works (STWs) into the oceans around coastal cities is well documented. However, there are fewer studies on the microplastic abundance in stormwater drains and their emissions into the coastal marine environment via sewage and stormwater drainage networks. Here, we comprehensively investigated microplastic abundance in 66 sewage and 18 sludge samples collected from different process stages at three typical STWs and 36 water samples taken from six major stormwater drains during the dry and wet seasons in Hong Kong, which is a metropolitan city in south China. The results showed that microplastics were detected in all the sewage and stormwater samples, with the abundance ranging from 0.07 to 91.9 and from 0.4 to 36.48 particles/L, respectively, and in all the sludge samples with the abundance ranging from 167 to 936 particles/g (d. w.). There were no significant seasonal variations in the microplastic abundance across all samples of sewage, sludge, and stormwater. For both waterborne sample types, a smaller size (0.02-0.3 mm) and fiber shape were the dominant characteristics of the microplastics. Polyethylene terephthalate (PET) and polypropylene (PP) were the most abundant polymer types in the sewage samples, while polyethylene (PE), PET, PP, and PE-PP copolymer were the most abundant polymer types in the stormwater samples. The estimated range of total daily microplastic loads in the effluent from STWs in Hong Kong is estimated to be 4.48 × 109 - 2.68 × 1010 particles/day, demonstrating that STWs are major pathways of microplastics in coastal environments despite the high removal percentage of microplastics in sewage treatment processes examined. This is the first comprehensive study on microplastics in the urban waters of a coastal metropolis. However, further studies on other coastal cities will enable an accurate estimation of the microplastic contribution of stormwater drains to the world's oceans.

Spatiotemporal occurrence of phthalate esters in stormwater drains of Hong Kong, China: Mass loading and source identification.

Urban stormwater is an important pathway for transporting anthropogenic pollutants to water bodies. Phthalate esters (PAEs) are endocrine disruptors owing to their estrogenic activity and potential carcinogenicity and their ubiquitous presence has garnered global interest. However, their transportation by urban stormwater has been largely overlooked. This study, for the first time, investigated 15 PAEs in stormwater from six major stormwater drains in the highly urbanized Hong Kong, a major metropolitan city in China. The results showed that PAEs were ubiquitous in the stormwater of Hong Kong, with total concentrations (∑15PAEs) spanning from 195 to 80,500 ng/L. Bis(2-n-butoxyethyl) phthalate (DBEP), diisopentyl phthalate (DiPP), dicyclohexyl phthalate (DCHP) and di-n-pentyl phthalate (DnPP) were detected in stormwater for the first time. Spatial variations in PAEs were observed among different stormwater drains, possibly due to the different land use patterns and intensities of human activities in their respective catchments. The highest and lowest levels of ∑15PAEs were found in Kwai Chung (3860 ± 1960 ng/L) and the Ng Tung River (672 ± 557 ng/L), respectively. Additionally, significantly higher concentrations of ∑15PAEs in stormwater were found in the wet season (2520 ± 2050 ng/L) than in the dry season (947 ± 904 ng/L). Principal component analysis classified domestic and industrial origins as two important sources of PAEs in the stormwater of Hong Kong. Stormwater played a crucial role in transporting PAEs, with an estimated annual flux of 0.705-29.4 kg. Thus, possible stormwater management measures were proposed to protect the receiving environment and local ecosystems from stormwater.

Widespread occurrence of emerging E-waste contaminants - Liquid crystal monomers in sediments of the Pearl River Estuary, China.

Liquid crystal monomers (LCMs), commonly used in screens of electronic devices, have recently been identified as a group of emerging chemicals of concern associated with e-waste. They are potentially persistent, bioaccumulative, and toxic substances, and may pose a threat to the marine ecosystem. The Pearl River Estuary (PRE) receives organic contaminants discharged from the Pearl River Delta region, where primitive handling of e-waste is widespread. However, information on the pollution status of LCMs in the PRE is absent. Herein, a rapid and robust analytical method was established using ultrasonic extraction, solid phase extraction cleanup, and GC-Orbitrap-MS analysis. The spatial distribution of 39 target LCMs was investigated in 45 surface sediment samples from the PRE. Ten LCMs were detected, with ΣLCMs ranged from 0.9 to 31.1 ng/g dry weight. Our results demonstrated a widespread occurrence of LCMs in the sediments of the PRE, and a gradient of their contamination from inshore to offshore regions, indicating land-based origins. Our reported ΣLCMs concentrations were relatively higher compared to many other legacy and emerging pollutants found in the same investigated area. Preliminary risk assessment showed 3VbcH, Pe3bcH and tFMeO-3bcHP might be the top 3 risk contributors in the PRE. Further investigation on the ecological impact of LCMs on marine benthic ecosystems, as well as identification of their sources and control measures are warranted.

Microplastic occurrence in the northern South China Sea, A case for Pre and Post cyclone analysis.

Microplastics (MPs) have become a great concern owing to their persistence and ecotoxicity in various environmental compartments. MPs can be transported from land to oceans via the aquatic system, and the oceans are believed to be the final sink for MPs. To resolve the lack of data concerning MP contamination in the northern South China Sea (NSCS), coastal seawater and sediments were investigated. The sample sites included the coastal area from Hong Kong to western Guangdong Province, which provided a representative coverage of variable distance to the shore. MP particles were observed in all samples, suggesting a widespread MP pollution in NSCS. The average MP abundance was relatively high in South China Sea, but it was lower than that in other Chinese coastal areas. In all samples, the dominant MP polymer was polyethylene terephthalate fibers. No statistically significant correlation was found between the abundances of MPs in seawater and sediment. The MP distribution in surface water affected by the monsoon exhibited high abundance in the east and low in the west, and MPs were more abundant near the shore than away from it. The tropical cyclone had no obvious effect on the overall MP abundance except in the Hong Kong west marine water (R4), which may attribute to proximity to Hong Kong and other islands.

Determination of As species distribution and variation with time in extracted groundwater samples by on-site species separation method.

It is challenging to dependably keep the native distribution of arsenic (As) species before sample analysis in the laboratory. The on-site separation method can avoid sample contamination and species change in the process of sample collection and transportation from field to laboratory. In this study, As species distribution and variation of the extracted groundwater was first analyzed by an on-site species separation method in Jianghan Plain, China. Our study illustrated that: 1) high-As groundwater generally existed under mildly reducing conditions (Eh < 200 mV), weak alkaline conditions (pH < 7.2), elevated concentrations of dissolved Fe(II) and S(-II), and high proportions of As (III); 2) As species in the groundwater changed dramatically at room temperature in 36 hours post extraction (HPE). Fe-sulfide and Fe oxides minerals, which adsorbed As (V), were the main reasons influencing the As species concentration; 3) Acidification and strong complexing agents cannot preserve As species effectively. The average proportion of As (III) in the wells, where groundwater samples from the depth of 25 m exceed 10 µg L-1 As, can be reduced by 61% and 63% after HCl and EDTA were added, respectively. Accurate assessment of concentrations and distribution variation of As species in groundwater can guide the removal of As and the safe use of water resources, especially in drought areas relying on drinking well water.

New insight on occurrence of liquid crystal monomers: A class of emerging e-waste pollutants in municipal landfill leachate.

Liquid crystal monomers (LCMs) have been proposed as a class of emerging organic pollutants, which were recently detected in indoor dust and sediment samples collected near electronic devices recycling facilities. However, there is a knowledge gap for analytical method, occurrence, and distribution of LCMs in aqueous sample. Herein, a robust method was developed to determine 38 target LCMs in landfill leachate. A combined ultrasonic enhanced liquid-liquid extraction, saponification and silica/florisil packed column purification method achieved recoveries of 76.9~127.1%, 84.5~114.6% and 81.3~104.6% at spiking levels of 2 ng, 10 ng and 50 ng in leachate, respectively. The developed method was validated through determination of target LCMs in leachate samples collected from municipal landfills in Hong Kong (HK) and Shenzhen (SZ), China. There were 23 and 20 LCMs detected in the HK (ΣLCMs=1120 ng/L) and SZ (ΣLCMs=409 ng/L) sample, respectively, with 6 LCMs newly detected in the environment. This study provided the first evidence suggesting that landfill leachate might be a potential sink of LCMs emitted from e-waste. Future study is urged to investigate the potential migration of LCMs from landfill leachate as a point source, and their occurrence, distribution, fate, and ecotoxicological risk in aquatic environments on regional and global scales.

The identification of halogenated disinfection by-products in tap water using liquid chromatography-high resolution mass spectrometry.

In this paper, a comprehensive method for the identification of the unknown halogenated DBPs (X-DBPs, X = Cl, Br, and I) in the tap water of Wuhan, China via liquid chromatography-high resolution mass spectrometry (LC-HRMS) was developed. 123 X-DBPs were identified through the stepwise procedure, 94 of them were newly identified, and 3 of them were confirmed by standards. Most X-DBPs were aliphatic compounds and highly unsaturated and phenolic compounds, some X-DBPs contained multiple halogen atoms and rich in carboxyl groups, such as C2H2O2BrCl, C2H2O2Br2, and C2H2O2ClI. It was worth noting that the concentration of some X-DBPs had the same trend with time. Most Cl-DBPs remained stable and I-DBPs were detected occasionally by monitoring the change of concentration of these X-DPBs with the time during three consecutive months. The results demonstrate that the proposed method could provide valuable molecular formula and structure information on unknown multiple halogenated DBPs, or be used for the identification of other multiple halogenated organic compounds in different media.

The effects of different inorganic salts on the structure and properties of ionic liquid plasticized starch/poly(butylene succinate) blends.

1-Butyl-3-methylimidazole chloride ([BMIM]Cl) plasticized starch/poly(butylene succinate) (PBS) blends containing inorganic salts with different cations were prepared by a Haake mixer. The compatibility, thermal behaviors including crystallinity, crystallization temperature and melting temperature, thermal stability, and mechanical properties of these blends were systematically investigated by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that the inorganic salts could interact strongly with [BMIM]Cl plasticized starch/PBS blends to improve their mechanical properties, while the thermal stability of the [BMIM]Cl plasticized starch/PBS blends was simultaneously reduced. The SEM results suggested that the compatibility of [BMIM]Cl plasticized starch and PBS was significantly improved with increasing inorganic salt content. Furthermore, by incorporating inorganic salts, the melting enthalpy (ΔH m), crystallinity (X c), and cold crystallization temperature (T cc) of the blends were decreased.