Aging increases the particulate- and leachate-induced toxicity of tire wear particles to microalgae.

The toxic effects of tire wear particles (TWPs) on organisms have attracted widespread concerns over the past decade. However, the underlying toxicity mechanism of TWPs, especially aged TWPs to marine microalgae remains poorly understood. This study investigated the physiological and metabolic responses of Phaeodactylum tricornutum to different concentrations of TWPs (Experiment 1), virgin and differently aged TWPs (Experiment 2) as well as their leachates and leached particles (Experiment 3). Results demonstrated that TWPs promoted the growth of microalgae at low concentrations (0.6 and 3 mg L-1) and inhibited their growth at high concentrations (15 and 75 mg L-1). Moreover, aged TWPs induced more profound physiological effects on microalgae than virgin TWPs, including inhibiting microalgae growth, decreasing the content of Chla, promoting photosynthetic efficiency, and causing oxidative damage to algal cells. Untargeted metabolomics analysis confirmed that aged TWPs induced more pronounced metabolic changes than virgin TWPs. This study represented the first to demonstrate that both particulate- and leachate-induced toxicity of TWPs was increased after aging processes, which was confirmed by the changes in the surface morphology of TWPs and enhanced release of additives. Through the significant correlations between the additives and the microalgal metabolites, key additives responsible for the shift of microalgal metabolites were identified. These results broaden the understanding of the toxicity mechanism of aged TWPs to microalgae at the physiological and metabolic levels and appeal for considering the effects of long-term aging on TWP toxicity in risk assessment of TWPs.

Influence of microplastics on the availability of antibiotics in soils.

Microplastics (MPs) and antibiotics, as two major types of emerging pollutants, inevitably coexist in the soil environment due to agricultural film residue, sewage irrigation and sludge application. However, the impact of MPs on antibiotic availability in soils with varying characteristics has not been extensively studied. Therefore, in this study, an interference experiment was conducted using three types of MPs (polyethylene (PE), polyvinyl chloride (PVC) and polypropylene (PP)) in red soil, paddy soil and cinnamon soil. The available antibiotics in soils were evaluated using diffusive gradients in thin-films (DGT). Results showed that MPs had a significant impact on the amount of antibiotics adsorbed on soil solid (Cs) by providing additional binding sites or altering soil characteristics (e.g., pH and dissolved organic carbon). The most significant effects on Cs were observed in cinnamon soil, and the Cs values were dependent on concentration of MPs. The available antibiotics, as measured by DGT significantly decreased after the addition of MPs. This decrease was influenced by the soil characteristics. However, the concentration of antibiotics in soil solutions (Cd) was only slightly impacted by MPs. Therefore, the influence of MPs on the migration of antibiotics was reflected by their impact on the soil/water partition coefficient (Kd), while the resupply ability (R) from the soil solid phase was less influential. Moreover, the dosage of MPs had a significant effect on the availability of antibiotics in CS by promoting the adsorption of antibiotics on the solid phase, while in RS and PS, the soil properties played a dominate role in the changes in antibiotic availability after MP addition. These results indicate that the impact of MPs on available antibiotics mainly depends on soil properties. In addition, DGT measurement is more sensitive than soil solution to investigate the effects of coexisting pollutants on the behavior of antibiotics in soil.

A machine learning-based QSAR model reveals important molecular features for understanding the potential inhibition mechanism of ionic liquids to acetylcholinesterase.

The broad application of ionic liquids (ILs) has been hindered by uncertainties surrounding their ecotoxicity. In this work, a Quantitative Structure-Activity Relationship (QSAR) model was devised to predict the inhibition of ILs towards the activity of AChE, employing both Random Forest (RF) and eXtreme Gradient Boosting (XGBoost) machine learning approaches. Fourteen kings of essential molecular feature descriptors were screened from an initial roster of 244 descriptors through the application of a feature importance index and they showed a significant impact on the activity of AChE activity. The two models based solely on the 14 most critical molecular descriptors could maintain model's robustness and reliability. The correlation analysis between these 14 descriptors and the inhibition of AChE activity revealed the potential impact of the molecular characteristics on ILs toxicity. The results underscored the main influence of cations in ILs on the inhibitory activity towards the AChE enzyme. Specifically, cations exhibiting hydrophobicity properties were found to exert more potent inhibitory effects on the AChE enzyme. In addition, some other properties of the cations, such as the degree of branching, atomic weight and partial charge also modulated their inhibition potential. This study enhances the comprehension of the structure-activity relationship between ILs and AChE inhibition, providing a reference for designing safer and greener ILs.

Measurement of perfluoroalkyl substances in drinking water sources by DGT sampler with a novel fluorinated graphite binding gel.

Extensive use of per- and polyfluoroalkyl substances (PFASs) has resulted in their widespread presence in natural waters. Concern for public health requires reliable measurement methods for determining their distribution and risks. Here, a sampling method based on diffusive gradients in thin films (DGT) was developed for measuring PFASs in drinking water sources. Fluorinated graphite (FG) particles were used to prepare the DGT binding gel for selective enrichment of trace PFASs in an aqueous environment. The FG-DGT method did not show sensitivity to relevant environmental parameters including pH (5.0-9.0), ionic strength (0.001-0.5 M), or DOM concentration (0-30 mg/L). The FG-DGT had enough capacity for deployment of up to four months. Six traditional and emerging PFASs including PFOS, PFOA, PFHpA, PFHxS, PFNA, and 6:2 FTSA at the ng/L level were detected in two major reservoirs serving as public drinking water sources by FG-DGT method coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS). PFOA appeared at the highest observed concentrations in the drinking water sources. The research demonstrates that FG-DGT is an effective and efficient tool for monitoring PFASs in drinking water.

Development and application of diffusive gradients in thin films for in situ sampling of the organic UV filter 4-methylbenzylidene camphor (4-MBC) in waters.

4-Methylbenzylidene camphor (4-MBC), a typical organic UV filter (OUVF) in personal care products, is considered to be a potential endocrine disruptor due to its estrogenic activity and bioaccumulation. Although 4-MBC residues have been extensively identified in aquatic waters, little is known about their occurrence, levels, and potential risk in coastal waters. This study developed a reliable sampling approach, based on diffusive gradients in thin films (DGT) with XAD-2 as the binding agent, for monitoring 4-MBC in coastal waters. The diffusion coefficients of 4-MBC in freshwater and artificial seawater were 3.65 × 10-6 cm2/s and 3.83 × 10-6 cm2/s, respectively. XAD-2 binding gel showed rapid adsorption to 4-MBC. The accumulated masses of 4-MBC in XAD-2 DGT increased linearly with deployed time for 7 days in freshwater and seawater, which agreed well with theoretical predictions. The sampling performance was independent of ionic strength (0.0001-0.5 M), pH (4.0-8.5), and dissolved organic matter (0-20 mg/L). Field deployment in the river estuary and bathing beach showed that DGT-measured 4-MBC concentrations were consistent in comparison with grab sampling. Environmental risk assessment showed that 4-MBC may pose a medium risk to aquatic organisms based on computed risk quotient (RQ) values. Sewage discharge is the main source of 4-MBC risk, while the residue in recreation beaches contributes more significantly in summer. The established DGT sampling is suitable for seasonal monitoring, source identification, and risk assessment of 4-MBC in coastal waters.

Methylparaben toxicity and its removal by microalgae Chlorella vulgaris and Phaeodactylum tricornutum.

The widespread occurrence of methylparaben (MPB) has aroused great concern due to its weak estrogenic endocrine-disrupting property and potential toxic effects. However, the degradation potential and pathway of MPB by microalgae have rarely been reported. Here, microalgae Chlorella vulgaris and Phaeodactylum tricornutum were used to investigate their responses, degradation potential and mechanisms towards MPB. MPB showed low-dose stimulation (by 86.02 ± 0.07% at 1 mg/L) and high-dose inhibition (by 60.17 ± 0.05% at 80 mg/L) towards the growth of C. vulgaris, while showed inhibition for P. tricornutum (by 6.99 ± 0.05%-20.14 ± 0.19%). The degradation efficiencies and rates of MPB were higher in C. vulgaris (100%, 1.66 ± 0.54-5.60 ± 0.86 day-1) than in P. tricornutum (4.3-34.2%, 0.04 ± 0.01-0.08 ± 0.00 day-1), which could be explained by the significantly higher extracellular enzyme activity and more fluctuation of the protein ratio for C. vulgaris, indicating a higher ability of C. vulgaris to adapt to pollutant stress. Biodegradation was the main removal mechanism of MPB for both the two microalgae. Furthermore, two different degradation pathways of MPB by the two microalgae were proposed. MPB could be mineralized and completely detoxified by C. vulgaris. Overall, this study provides novel insights into MPB degradation by microalgae and strategies for simultaneous biodegradation and detoxification of MPB in the environment.

Development of diffusive gradients in thin film technique for seasonal monitoring of benzophenone-type UV filters in coastal waters.

Benzophenone(BP)-type UV filters are continuously released into various aquatic environments via the effluent discharge of wastewater treatment plants (WWTPs) and recreational activities in coastal beaches. In this study, we developed a robust and reliable sampling approach, diffusive gradients in thin-films (DGT), for seasonal monitoring of six BP derivatives in coastal waters to investigate their occurrence and environmental risk. The binding capacities of both XAD-2 and HLB gels for test BPs were over 252 µg with no significant deterioration in marine environment, suggesting that theoretically, DGT is capable of sampling for at least 3 months effectively. The diffusion coefficients of BPs in freshwater and seawater were determined for the first time. The sampling performance showed no dependence on environmental conditions including pH (4.0-8.5), ionic strength (0.0001-0.5 M) and dissolved organic matter (0-20 mg L-1). The developed DGT samplers were successfully applied in a river estuary linked to a WWTP and a bathing beach at different periods of one year. Results showed that the concentrations of BPs in the coastal waters were dependent on seasonal variation. The highest level in summer and the ecological risk should be considered based on the risk quotient values. These results demonstrated that the present DGT method is suitable for measuring, characterization, and risk assessment of BPs in freshwater and marine environment.

Simultaneous evaluation of kinetic release of labile arsenic and phosphorus in agricultural soils using cerium oxide-based DGT.

The adsorption/desorption of arsenic (As) in agricultural soils is of utmost importance for the evaluation of its kinetic release and potential of entering the food chain by uptake of crops. However, the mobility of As in soils is closely related to the migration behavior of soil phosphorus (P) due to their chemical similarity. Here, the distribution and desorption kinetics of As and P in four different types of farmland soils were simultaneously estimated by cerium oxide-based diffusive gradients in thin films technique (CeO2-DGT) coupled with dynamic model of DGT induced fluxes in soils (DIFS). CeO2-DGT was deployed in the soils over 400 h to investigate the interactions between As and P for their migration behaviors. The accumulated masses of As in the DGT devices showed reverse orders with those of P among the four soils, indicating their competitive adsorption on soil solids. The distribution coefficients (Kdl) for the labile As and P derived from the DIFS model were mutually exclusive. Clay in the soil reduced the pool size of the labile As by increasing the irreversible adsorption of As on soil particles. The adsorption rate constants of As were much smaller than P but their desorption rate constants were comparable. Among the four soils, the soil with the highest soil labile As/P molar ratio measured by DGT showed the largest potential of As phytotoxicity. Both As and P could reach the equilibrium of resupply within 0.7- 18 min under DGT depletion, and significant negative correlation was observed between the desorption rate (kb) of As and clay content in the soils.

In situ measurement of synthetic musks in wastewaters using diffusive gradients in thin film technique.

Synthetic musks (SMs) are used extensively in household and personal care products and have acted significant concerns due to their environmental impacts and potential health effects. Here, we present a passive sampling approach based on diffusive gradients in thin films (DGT) for in situ measurement of SMs in urban wastewaters. XAD-2 binding gel, which has a rapid binding rate and high elution efficiency, was used in DGT device for the accumulation of six polycyclic musks and three nitro musks. The diffusion coefficients (D and DNL) of the SMs through agarose gel without and with a nylon filter membrane were 3.37-4.49 and 1.48-4.41 ×10-6cm2 s-1. The filter membrane caused an ~3 h lag phase and slowed the diffusion rates of the SMs through the diffusive phase. Solution pH (4.30-8.92), ionic strength (0.0001-0.5 M) and dissolved organic matter (0-20 mg L-1) showed no obvious influence on uptake of the SMs in DGT. The measured average SM concentrations in the effluent of wastewater treatment plants ranged from 0.45-696 ng/L for DGT deployment, without obvious membrane biofouling, and they were comparable to the concentrations determined by grab sampling. These results confirmed that the present method is reliable and convenient for in situ measurement of semivolatile hydrophobic SMs in complicated waters and is an available tool to investigate the environmental behaviors of SMs in the environment.

Ceria oxide nanoparticle-based diffusive gradients in thin films for in situ measurement of dissolved reactive phosphorus in waters and sewage sludge.

A passive sampling method based on diffusive gradients in thin films (DGT) using ceria oxide (CeO2) binding gel was developed for in situ measurement of dissolved reactive phosphorus (DRP). CeO2-based DGT showed excellent uptake performance for DRP, and the uptake mass was consistent with the predication by DGT equation. pH (4.2~9.4) and ionic strength (0.01~500 mM) had no effects on the uptake of DRP. Filed deployment of CeO2-DGT in reservoir water and seawater showed that the measureable concentrations of DRP were comparable to those obtained by grab sampling. CeO2-DGT was deployed in sewage sludge, and results showed the ratios (RS) between the concentration (CDGT) by CeO2-DGT and the concentration (CS) obtained by a traditional centrifugation method ranged from 0.23 to 0.58. This result indicated that sludge solid phase was a potential pool of DRP in sludge solution, and the DRP released from sludge solid phase could compensate partly the consumption of DRP at the interface of DGT device during the deployment. The ratios RS had positive correlation with the content of Fe (r = 0.847, p < 0.01) but were reversed with the level of Ca (r = - 0.879, p < 0.01) in sewage sludge. The proposed method provided a powerful tool for in situ measurement of DRP in natural waters and for release behavior of DRP in sludge.

Desorption kinetics of tetracyclines in soils assessed by diffusive gradients in thin films.

Tetracyclines (TCs) are frequently detected in agricultural soils worldwide, causing a potential threat to crops and human health. In this study, diffusive gradients in thin films technique (DGT) was used to measure the distribution and exchange rates of three TCs (tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC)) between the solid phase and solution in five farmland soils. The relationship between the accumulated masses with time suggested that TCs consumption in soil solution by DGT would induce the supply from the soil solid phase. The distribution coefficient for the labile antibiotics (Kdl), response time (Tc) and desorption/adsorption rates (kb and kf) between dissolved and sorbed TCs were derived from the dynamic model of DIFS (DGT induced fluxes in soils). The Kdl showed similar sizes of labile solid phase pools for TC and OTC while larger pool sizes were observed for CTC in the soils. Although the concentrations of CTC were lowest in soil solution, the potential hazard caused by continuous release from soil particles could not be ignored. The long response time (>30 min in most cases) suggested that the resupply of TCs from soil solids was limited by their desorption rates (1.26-121 × 10-6 s-1). The soils in finer texture, with higher clay and silt contents (<50 µm) showed a greater potential for TCs release.

Development of cerium oxide-based diffusive gradients in thin films technique for in-situ measurement of dissolved inorganic arsenic in waters.

A diffusive gradients in thin films (DGT) method using a new high-capacity cerium oxide (CeO2) binding gel, for the first time, was developed for measuring dissolved inorganic arsenic in freshwater and seawater. The capacities of the new CeO2 binding gel were 682 µg and 375 µg for AsIII and AsV, respectively. The masses of AsIII and AsV accumulated by CeO2-DGT device increased linearly with time and agreed well with the theoretical value calculated by DGT equation. The arsenic accumulation by CeO2-DGT was independent of pH (4.05-9.04) and ionic strength (0.1-750 mM), and common anions including CO32-, SO42-, Cl- and PO43- had no obvious interference. CeO2-DGT showed excellent long-term deployment performance in freshwater and synthetic seawater. Field trials with CeO2-DGT achieved successfully the time-weighted-average concentrations of total inorganic arsenic in reservoir water (1.38 ±â€¯0.09 µg/L) and coastal seawater (0.45 ±â€¯0.06 µg/L). The results were comparable to those measured by grab sampling. The proposed method was reliable and robust for in-situ measurements of dissolved inorganic arsenic in environmental waters.

Diffusive gradients in thin films based on MOF-derived porous carbon binding gel for in-situ measurement of antibiotics in waters.

Diffusive gradients in thin films (DGT) can achieve the time-weighted-average (TWA) concentrations of analytes in the period of deployment. Here we developed an approach based on DGT with a novel binding gel using porous carbon material (PCM) derived from metal-organic framework (MOF) for in-situ measurement of antibiotics in water samples. The diffusion coefficients of 20 antibiotics (nine sulfonamides, ten fluoroquinolones, and trimethoprim) in agarose diffusive gel were 1.41 × 10-6 cm2/s to 4.75 × 10-6 cm2/s at 25 °C. The capacity of PCM binding gel toward the antibiotics was ~100 µg per gel disc. The masses of the antibiotics accumulated by PCM-based DGT increased linearly with time, and they were almost independent of pH (4.2-8.4) and ionic strength (1-500 mM). The performance of the novel DGT was evaluated using freshwater and synthetic seawater spiked with the antibiotics in laboratory. The results showed good agreement with the theoretical predications except sulfacetamide. The detection limits achieved by the DGT with three devices together for deploying up to seven days were 1.0-18.0 ng/L. Field deployment in municipal wastewater treatment plant effluent and seawater showed that the TWA concentrations of antibiotics were 3.8-1342.5 ng/L and 5.6-43.3 ng/L, respectively, which were comparable to those measured by grab sampling. The proposed DGT was an efficient tool for the measurement of antibiotics in environmental waters.

Preparation of polydopamine-coated graphene oxide/Fe3O4 imprinted nanoparticles for selective removal of fluoroquinolone antibiotics in water.

Antibiotics in water have recently caused increasing concerns for public health and ecological environments. In this work, we demonstrated polydopamine-coated graphene oxide/Fe3O4 (PDA@GO/Fe3O4) imprinted nanoparticles coupled with magnetic separation for fast and selective removal of fluoroquinolone antibiotics in water. The nanoparticles were prepared by the self-polymerization of dopamine using sarafloxacin as a template. The imprinted PDA film of 10~20 nm uniformly covered the surface of GO/Fe3O4 providing selective binding sites. The nanoparticles showed rapid binding and a large capacity (70.9 mg/g). The adsorption data fitted well the Langmuir and pseudo-second order kinetic equations. The nanoparticles could be easily separated by a magnet following the adsorption and then regenerated by simple washing for repetitive adsorptions. The nanoparticles were successfully used for the removal of fluoroquinolone antibiotics in seawater, with removal efficiencies of more than 95%. The proposed strategy has potentials for efficient removal of antibiotics in environmental water.