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While research on the aging behavior of plastics in aquatic systems is extensive, studies focusing on high-altitude ecosystems, characterized by higher solar radiation and lower temperatures, remain limited. This study investigated the long-term aging behavior of non-biodegradable plastics (non-BPs), namely polyethylene terephthalate (PET) and polypropylene (PP) and biodegradable plastics (BPs), specifically polylactic acid plus polybutylene adipate-co-terephthalate (PLA + PBAT) and starch-based plastic (SBP), in a tributary of the Yarlung Zangbo River on the high-altitude Tibetan Plateau. Over 84 days of field aging, all four types of plastics exhibited initial rapid aging followed by deceleration. This aging process can be divided into two phases: rapid surface oxidation aging and an aging plateau phase. Notably, PP aged at a rate comparable to BPs, contrary to expectations of faster aging for BPs. Compared to low-altitude aquatic ecosystems, plastics in this study showed a faster aging rate. This was primarily due to intense ultraviolet radiation causing severe photoaging. Furthermore, the lower temperatures contributed to the formation of thinner biofilms. These thinner biofilms exhibited a reduced capacity to block light, further exacerbating the photoaging process of plastics. Statistical analysis results indicated that temperature, total nitrogen TN, and total phosphorus TP were likely the main water quality parameters influencing plastic aging. The varying effects of water properties and nutrients underscore the complex interaction of water quality parameters in high-altitude environments. Given the delicate nature of the high-altitude environment, the environmental impact of plastics, especially BPs, warrants careful consideration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Tire wear particles (TWP) represent a distinctive form of microplastics (MPs) that are widely distributed in aquatic ecosystems. However, the toxicity of various types of TWP on phytoplankton remain to be further explored. Thus, three different TWPs originating from replaced bicycle, car, and electro-mobile tire (marked as BTWP, CTWP, and ETWP) were selected and their long-term biological influences on Chlorella vulgaris were investigated. Results demonstrated TWPs showed a concentration-dependent growth promotion of Chlorella vulgaris, with a maximum promotion rate reached to 40.51 % (10 mg/L, 10 d), 23.5 % (80 mg/L, 12 d), and 28.7 % (20 mg/L, 12 d) in the presence of BTWP, CTWP and ETWP, respectively. Meanwhile, TWPs could stimulate the secretion of EPS and induce oxidative stress. EPS analysis revealed the increase of polysaccharides could protect the cell from the direct contact with TWP particles. Moreover, the increased concentration of EPS also helps to induce the settlement of TWP and reduce the leachate release. The release of TWP into the environment could act as an accelerator for the growth of Chlorella vulgaris, which might further change the normal physicochemical behaviors of algae colony in aquatic system. Our findings provide new insights into the toxicity mechanism of TWPs on freshwater algae and valuable data on environmental risk assessment of TWPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Identifying priority pollutants in wastewater treatment plant (WWTP) effluents is crucial for optimizing monitoring efforts, improving regulations, and developing targeted mitigation strategies. Despite the presence of numerous trace organic pollutants in WWTP effluents, a comprehensive prioritization scheme is lacking, hindering effective control. This study screened 216 micropollutants, including pharmaceuticals, pesticides, and industrial chemicals, which had been detected in effluents from 46 WWTPs across China. A multi-criteria prioritization method was developed, considering exposure potential based on median concentrations and detection frequencies, as well as hazard potential determined by persistence, bioaccumulation, in vitro toxicity, and in vivo toxicity. Pollutants with low exposure or hazard potential were filtered out, and a priority index was calculated to rank the remaining 59 substances. The top 15 priority pollutants included regulated persistent organic pollutants like perfluorooctanoic acid and their alternatives such as perfluorobutane sulfonate, pesticide transformation products, and emerging contaminants such as bisphenol A, which are not currently regulated in WWTP effluents. This study provides a systematic approach to identify priority pollutants and generates a guiding framework for monitoring, regulation, and control of both well-recognized and overlooked contaminants in WWTP effluents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microplastics (MPs) and fluoxetine are ubiquitous emerging pollutants in aquatic environments that may interact with each other due to the carrier effects of MPs, posing unpredictable risks to non-target organisms. However, limited studies have focused on the carrier effects of MPs in the aquatic food chain. This study evaluated the influences of polystyrene MPs on the trophic transfer and biotoxicity of fluoxetine in a simple food chain composed of brine shrimp (Artemia nauplii) and zebrafish (Danio rerio). The finding reveals that carrier effects of MPs enhanced the accumulation of waterborne fluoxetine in brine shrimp, but suppressed that in zebrafish due to the distinct retention times. The accumulated fluoxetine in shrimp was further transferred to fish through the food chain, which was alleviated by MPs due to their cleaning effects. In addition, the specific neurotransmission biotoxicity in fish induced by fluoxetine was mitigated by MPs, whilst the oxidative damage, apoptosis, and immune responses in zebrafish were reversely enhanced by MPs due to the stimulating effect. These findings highlight the alleviating effects of MPs on the trophic transfer and specific biotoxicity of fluoxetine in the food chain, providing new insights into the carrier effects of MPs in aquatic environments in the context of increasing global MP pollution., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The transport of nanoplastics (NPs) in porous media has received a lot of attention, but the studies on the long-term release of NPs retained in porous media and the particle fracture during this process are seriously lacking. For filling this deficiency, we examined the individual or synergistic effects of surfactants, natural organic matters (NOMs), antibiotics, and bacteria on the desorption, long-term release, and particle fracture behaviors of polystyrene NPs (PS-NPs) retained in porous media. It was found that the change in hydrophilicity of PS-NPs dominated the long-term release of PS-NPs retained in porous media when surfactants were present. In the single system of surfactants and the dual system of surfactants and NOMs, the release of PS-NPs were improved owing to the increasing hydrophilicity of PS-NPs, although cationic surfactants also reduced the electrostatic repulsion between PS-NPs and porous media. Increasing antibiotic concentration reduced the electrostatic repulsion between PS-NPs and porous media to inhibit the release of PS-NPs. When bacteria were present whether containing antibiotics or not, the effects on roughness of PS-NPs dominated the release of PS-NPs. The effects of surfactants and NOMs on the PS-NP desorption were similar with the long-term release, with changes in hydrophilicity dominating the process. Whereas the effects of antibiotics and bacteria on the PS-NP desorption were different with the long-term release. Surfactants and NOMs in the presence of surfactants inhibited the fracture of PS-NPs by increasing the hydrophilicity of PS-NPs brought about the coating of water molecules on PS-NPs for protection. Antibiotics had no significant effects on the fracture of PS-NPs due to unaltered vertical forces on PS-NPs and no protective effect. Bacteria in the presence or absence of antibiotics inhibited the fracture of PS-NPs by coating PS-NPs retained in porous media to protect PS-NPs from fracture., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The release of antibiotics has attracted wide attention due to their abuse and discharge. How to remove these emerging contaminants is an urgent need to be solved. In the present study, sludge-based biochar combining chitosan and iron oxide was prepared via municipal sewage sludge. The novel biochar modified with chitosan and iron oxide exhibited satisfying performance in eliminating antibiotics from water. The application of modified biochar combined with activated persulfate (PS) showed a remarkable removal efficiency of 96.98% for tetracycline (TC). Analysis of the surface characteristics of the modified biochar showed the presence of structural defects, dispersed iron oxides, abundant functional groups, a porous structure, and a relatively stable crystal structure. These characteristics attributed significant importance to facilitating the degradation of TC. A series of experimental conditions including preparation temperature (600-900 ℃), reaction temperature (15-45 ℃), contaminant concentration (30-180 mg/L), adsorbent usage (0.1-1 g/L), pH (2-10), and persulfate addition concentration (1-5 mmol) were conducted. The results revealed that the highest removal efficiency was achieved at 96.98% under the conditions of TC concentration at 30 mg/L, reaction temperature at 35 ℃, pH of 4, adsorbent addition amount of 0.6 g/L, and PS concentration of 2 mmol, respectively. Three degradation pathways and seven intermediate products of TC were proposed. Therefore, our study provides a promising approach for developing effective removal of antibiotic pollutants., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Majority zero-valent iron (ZVI) materials are prepared by reducing agents in liquid phase, resulting in the high environmental pollution and poor particle size distribution uniformity. Therefore, this study employed a green synthesis method to prepare ZVI. Tannins (TA) with phenolic hydroxyl groups that are characterized by strong reducing capacity were employed to synthesize ZVI (TA@ZVI). The dispersity and stability of ZVI was improved by TA, which inhibited the agglomeration of ZVI. Meanwhile, the specific surface area of TA@ZVI was higher than chemical prepared ZVI, increasing the reactive sites. The organic matter components enriched on TA could promote the adsorption of pollutants and complex with Fe(II/III) to enhance the reactivity of TA@ZVI. Also, the polyphenol structure in TA was oxidized to quinone, which facilitated electron transport. In order further test the performance of TA@ZVI, SMX was chosen as a target pollutant to study the oxidative degradation performance of TA@ZVI. SO 4 •- degraded about 16.4%-25.5% SMX and •OH degraded about 49.8%-63.9% SMX in the pH range of 4-6 while •OH played a dominant role in the neutral and alkaline conditions. Moreover, the presence of TA reduced Fe(III) to Fe(II) and promoted the release of Fe(II), providing a continuous source of •OH for the oxidative degradation of SMX. Besides, the conversion of Fe(II/III) was accelerated due to TA, which delayed the formation of passivation layer. Thus, TA enhanced the antioxidant capacity of ZVI. Generally, this study provided an environmental-friendly technology to synthesize and improve the reactivity of ZVI., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Recycling of Au(III) from wastewater can not only increase resource utilization but also reduce environmental pollution. Herein, a chitosan-based bio-adsorbent (DCTS-TA) was successfully synthesized via crosslinking reaction between tannin (TA) and dialdehyde chitosan (DCTS) for the recovery of Au(III) from the solution. The maximum adsorption capacity for Au(III) was 1146.59 mg/g at pH 3.0, which fitted well with the Langmuir model. The XRD, XPS, and SEM-EDS analyses demonstrated that Au(III) adsorption on DCTS-TA was a collaborative process involving electrostatic interaction, chelation, and redox reaction. Existence of multiple coexisting metal ions did not significantly affect the Au(III) adsorption efficiency, with >90 % recovery of DCTS-TA obtained after five cycles. DCTS-TA is a promising candidate for Au(III) recovery from aqueous solutions due to its easy preparation, environmental-friendliness, and high efficiency., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Chemical sulfidation has been considered as an effective strategy to improve the reactivity of zero-valent iron (S-ZVI). However, sulfidation is a widespread biogeochemical process in nature, which inspired us to explore the biogenetic sulfidation of ZVI (BS-ZVI) with sulfate-reducing bacteria (SRB). BS-ZVI could degrade 96.3% of trichloroethylene (TCE) to acetylene, ethene, ethane, and dichloroethene, comparable to S-ZVI (97.0%) with the same S/Fe ratio (i.e., 0.1). However, S-ZVI (0.21 d -1 ) exhibited a faster degradation rate than BS-ZVI (0.17 d -1 ) based on pseudo-first-order kinetic fitting due to extracellular polymeric substances (EPSs) excreted from SRB. Organic components of EPSs, including polysaccharides, humic acid-like substances, and proteins in BS-ZVI, were detected with 3D-EEM spectroscopy and FT-IR analysis. The hemiacetal groups and redox-activated protein in EPS did not affect TCE degradation, while the acetylation degree of EPS increased with the concentration of ZVI and S/Fe, thus inhibiting the TCE degradation. A low concentration of HA-like substances attached to BS-ZVI materials promoted electron transport. However, EPS formed a protective layer on the surface of BS-ZVI materials, reducing its TCE reaction rate. Overall, this study showed a comparable performance enhancement of ZVI toward TCE degradation through biogenetic sulfidation and provided a new alternative method for the sulfidation of ZVI.

The use of biochar materials as catalysts to activate persulfate (PS) for the degradation of antibiotics has attracted much attention. In this study, a carbonaceous material (Cu/Zn-SBC) was prepared from sewage sludge by hydrothermal modification. The efficiency of PS activation by Cu/Zn-SBC was investigated using tetracycline (TC) as the model antibiotic. In the Cu/Zn-SBC + PS system, the TC removal rate reached 90.13% at 10 min and exceeded 99% within 4 h. This not only met the requirement of removing large amounts of pollutants in a short time but also achieved the complete removal of pollutants in the subsequent time. Additionally, the Cu/Zn-SBC + PS system was found to be dominated by radical and nonradical pathways. Cu, hydroxyl and carboxyl groups on the surface of Cu/Zn-SBC promoted the production of free radicals and non-free radicals. Under several changes in reaction conditions and water environment factors, the TC removal rate remained above 85% within 10 min. Furthermore, the removal rate of TC was still 85.79% when Cu/Zn-SBC combined with PS was reused twice and 77.14% when reused four times. This study provides an ideal solution for the treatment of sewage sludge, and offers a stable and efficient material for removing antibiotics from wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Many aging experiments on microplastics (MPs) have been carried out using UV radiation or strong oxidants. Little attention has been paid to the role of water environmental factors such as dissolved organic matter (DOM). In this study, the role of fulvic acid (FA), the main component of DOM, in the UV-aging process of MPs was explored. MPs aged under UV, and UV along with 0.5 mg/L and 2 mg/L FA, were selected as subjects. The results showed that (1) FA accelerated the aging process of polyethylene (PE). PE aged with FA had a larger specific area (S BET ), with more holes and cracks on the surface. (2) FA enhanced the adsorption capacity of PE. The TC adsorption quantities of 0, 0.5, and 2 mg/L FA-aged PE were 1.100, 1.447, and 1.812 mg/L, respectively. (3) The quantity of TC desorbed by PE increased, whereas the desorption rate decreased as the FA concentration increased. The desorption rates of TC at 0, 0.5, and 2 mg/L FA-aged PE were 25.16%, 22.05%, and 19.52% in water, and 72.10%, 70.36%, and 59.51% in simulated intestinal fluid. This study explored the role of FA in the aging process of MPs. Moreover, research on the aging mechanism of MPs is enriched., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The formation of plastisphere on plastics and their potential impact on freshwater ecosystems have drawn increasing attention. However, there is still limited information about the effects of plastisphere on the heavy metal adsorption capacity and the related mechanism of plastic debris in different freshwaters. Herein, the trace metal adsorption capacity, kinetics and adsorption mechanisms of virgin and biofilm-covered plastic debris were investigated. Polypropylene (PP) and polyethylene terephthalate (PET) plastic debris were placed in three freshwaters (Xuanwu Lake, Donghu Lake and the Qinhuai River) for 45 days to incubate biofilms. Batch adsorption experiments were performed to compare the adsorption processes of trace metal on virgin and biofilm-covered plastics. Results showed that biofilms increase the adsorption of metals on plastics, and the adsorption isotherms were well fitted by the Langmuir model. Furthermore, the adsorption capacities for lead (Pb(II)) were higher than that of cadmium (Cd(II)) and zinc (Zn(II)), with 256.21 and 277.38 μg/g (Pb(II)) adsorbed in biofilm-covered PP and PET, respectively, in Xuanwu Lake. The adsorption kinetics of metals on plastic debris were significantly affected by the biofilms, by switching the intraparticle diffusion for virgin plastic debris to film diffusion for the biofilm-covered plastic debris. Moreover, the complexation of functional groups within the biofilms might mainly contribute to the increases of metal adsorption, involving the participation of oxygen and nitrogen groups. Overall, these results suggested that biofilms reinforce the potential role of plastics as a carrier of trace metals in freshwaters.

The application of zero-valent iron (ZVI) is limited due to passivation and agglomeration. Therefore, biochar loading (MB) and biogenetic sulfidation via sulfate-reducing bacteria (SRB) were used to improve the reactivity of ZVI (BS-ZVI@MB) towards tetracycline (TC) degradation. Biochar provided more attachment sites for ZVI and SRB, thus alleviating the agglomeration. Additionally, quinone groups on biochar enhanced the electrons transfer through the measurement of electron donating/accepting capacities, and biogenetic sulfidation could inhibit the surface passivation of ZVI. Fe(Ⅱ/Ⅲ) produced after the addition of BS-ZVI@MB could complex with the A ring in TC to form Fe(Ⅱ/Ⅲ)-TC, which brought the oxidation of TC by complexed Fe(Ⅲ). Reactive oxygen species (ROS)(primarily •OH) were generated during the oxidation of Fe(Ⅱ), so as to promote the TC degradation. Extracellular polymeric substances (EPS) secreted from SRB had a slight quenching effect on ROS. Meanwhile, EPS formed a protective layer with Fe(Ⅱ/Ⅲ) on BS-ZVI@MB, reducing its reactivity with TC. Overall, this study showed an efficient modification technology of ZVI by biogenetic sulfidation and biochar loading for TC degradation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Recently, there is an increasing concern regarding the toxicity of nanoplastics (NPs) on freshwater organisms. However, knowledge about the potential impacts of NPs with different surface modification on freshwater biofilms is still very limited. In this research, biofilms were cultured in lab and exposed to nano polystyrene (PS) beads: non-functionalized PS NPs, PS-COOH NPs, and the carbon source utilization of biofilms were measured by BIOLOG ECO microplates. The results showed that both two types of PS NPs significantly reduced the total carbon metabolic activity of biofilms, compared with the controls, whereas the carbon metabolic rate increased notably, especially for the PS-COOH NPs treatments at day 14. Moreover, results from six categories of carbon sources analysis suggested that PS NPs with different surface chemical properties exhibit distinct effects on the carbon utilization of biofilms, and the divergent changes of the specific carbon source category were observed at day 21 from the two PS NPs treatments. In addition, the metabolic functional diversity of biofilms were not altered by the PS NPs treatments. These findings highlighted that chemical properties of NPs play an important role in the toxic effects on the carbon metabolism activities of the biofilms. This study offers new insights that nanoplastics of different chemical characteristics have the ability to affect the microbial-mediated carbon cycling process in aquatic ecosystems.

Sulfidated zero-valent iron (S-ZVI) is commonly used to degrade trichloroethylene (TCE). The reactivity of S-ZVI is related to not only the properties of S-ZVI but also the geochemical conditions in groundwater, such as coexisted NO 3 - . Therefore, the effect of NO 3 - on TCE degradation by S-ZVI and its mechanism were systematically studied. 95.17% of TCE was degraded to acetylene, dichloroethene, ethene, ethane and multi‑carbon products via β-elimination by fresh S-ZVI that contained 85.31% Fe 0 and 14.69% FeS in the presence of NO 3 - , demonstrating that NO 3 - did not affect the degradation pathway of TCE. While high concentration of NO 3 - (> 10 mg/L) competed for electrons at the Fe/FeO x interface with degradation products, leading to a continuous rising of acetylene. Moreover, the rapid reduction of NO 3 - to NH 4 + (89.79%) at the Fe 0 interface contributed to the release of 5.08 mM Fe 2+ from S-ZVI, which promoted the formation of Fe 3 O 4 with excellent electron conduction properties on the surface of S-ZVI. Accordingly, NO 3 - improved the degradation and electron selectivity of TCE by 51.07% and 2.79 fold, respectively. This study demonstrated that S-ZVI could remediate the contamination of NO 3 - and TCE simultaneously and the presence of NO 3 - could effectively enhance the degradation of TCE in groundwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Aggregation behaviors of bare, and sodium polyacrylate (PAA) and starch modified zero-valent-iron nanoparticles (nZVI), as well as their effects on the Cr (VI) removal were investigated by simulating the groundwater. Results showed that increased concentration of PAA (1-6 wt%) and starch (0.1-0.6 wt%) alleviated the aggregation of modified nZVI (abbreviated as P-nZVI and S-nZVI), while there was an optimum dosage of 4 wt% PAA and 0.3 wt% starch for the Cr (VI) removal, respectively. Moreover, as one of the fundamental water chemistry parameters, Ca 2+ (0, 5, and 10 mg L -1 ) greatly promoted the aggregation of modified nZVI, and decreased the Cr (VI) removal efficiency by them via forming bidentate bridging structure (between Ca 2+ and PAA) or complexes (between Ca 2+ and starch). Additionally, fulvic acid (FA) (0, 2, 5, and 10 mg L -1 ) decreased the Cr (VI) removal by P-nZVI because of the significantly improved electronic repulsion. However, FA enhanced the aggregation of S-nZVI, but diminished its performance on Cr (VI) removal due to the bridging effect between FA and starch. The present study was of great importance in predicting the migration of nZVI and contaminants removal under complex geological conditions in groundwater., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

There is an increasing concern regarding the potential effects of nanoplastics (NPs) on freshwater ecosystems. Considering the functional values of biofilms in freshwater, knowledge on whether and to what extent NPs can influence the ecosystem processes of biofilms were still limited. Herein, the freshwater biofilms cultured in lab were exposed to 100 nm polystyrene NPs (PS-NPs) of different dosages (1 and 10 mg/L) for 14 days. Confocal laser scanning microscope observation indicated that biofilms were dominated by filamentous, and spiral algae species and the intensity of extracellular polymeric substances increased under PS-NPs exposure. GeoChip 5.0 analysis revealed that PS-NPs exposure triggered a significant increase in functional genes α diversity (p < 0.05) and altered biofilms' functional structure. Furthermore, the abundance of genes involved in the total carbon and nitrogen cycling were increased under PS-NPs exposure. The abundance of nitrogen fixation genes experienced the most pronounced increase (24.4%) under 1 mg/L PS-NPs treatment, consistent with the increase of ammonium in overlying water. Whereas antibiotic resistance genes and those related to photosynthetic pigments production were suppressed. These results provided direct evidence for PS-NPs' effects on the biofilm functions in terms of biogeochemical cycling, improving our understanding of the potentials of NPs on freshwater ecosystems., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Microbial biofilms can rapidly colonize plastic debris in aquatic environments and subsequently, accumulate chemical pollutants from the surrounding water. Here, we studied the microbial colonization of different plastics, including polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride (PVC), and polyethylene (PE) exposed in three freshwater systems (the Qinhuai River, the Niushoushan River, and Donghu Lake) for 44 days. We also assessed the biofilm mass and associated metals attached to plastics. The plastics debris characteristics, such as contact angle and surface roughness, greatly affected the increased biofilm biomass. All types of metal accumulation onto the plastic substrate abundances significantly higher than the concentrations of heavy metal in the water column, such as Ba (267.75 μg/g vs. 42.12 μg/L, Donhu Lake), Zn (254 μg/g vs. 0.023 μg/L the Qinhuai River), and Cr (93.75 μg/g vs. 0.039 μg/L, the Niushoushan River). Compared with other metals, the heavy metal Ba, Cr and Zn accumulated easily on the plastic debris (PET, PP, PVC, and PE) at all incubation sites. Aquatic environmental factors (total nitrogen, total phosphorus, and suspended solids concentrations) largely shaped metal accumulation onto plastic debris compared with plastic debris properties., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Although the pollution of freshwater systems by microplastics and the resulting ecological effects have attracted widespread attention from scholars at home and abroad, the fragmentation of different types of microplastics in the natural environment has not yet received enough attention. To analyze the fragmentation processes and products of different types of microplastics, a 40 d natural light fragmentation experiment was carried out using four microplastics commonly found in water:polystyrene (PS), low-density polyethylene (LDPE), polypropylene (PP), and polyhydroxybutyrate (PHB). The pH, ORP, EC, and DO of the four types of plastic-aging liquids changed significantly during the aging process. During the weathering process, cracks and pores formed on the surface of LDPE and were later identified through scanning electron microscopy. Fourier transform infrared spectrometry indicated that the carbonyl index of LDPE increased the most in the experiment (an increase of 31.48%), suggesting that PP experienced significant aging. Dissolved organic carbon (DOC), a product of microplastics fragmentation, increased as weathering time progressed, and the concentration of DOC increased significantly after weathering for about 40 d. Compared with the baseline value, the concentration of DOC from PHB, PP, and LDPE in the leaching solution increased significantly, by 61.29%, 69.49%, and 89.15%, respectively. These results suggest that evident aging of microplastics in natural aquatic environments releases significant amounts of dissolved organic matter, and the ecological effects of this should be the subject of future research.

Microplastics (MPs) have frequently been detected in freshwater environments, and there is growing concern about their ecological effects, especially the influence of the "plastisphere" on the freshwater ecosystems. The colonization of microbes on MPs would significantly alter their transport behavior, i.e., buoyancy, in fresh water. In this research, we studied the effects of biofilm colonization on the sinking and floating of three MPs, i.e., polyethylene terephthalate (PET), polypropylene (PP), and polyvinyl chloride (PVC), after 44 days of incubation in three freshwater systems (the Niushoushan River, the Qinhuai River, and East Lake) in China. The results showed that the biofilms attached to the three MPs contained different biomass and chlorophyll-a levels were related to water environmental conditions and physicochemical properties of MPs, based on redundancy analysis. Generally, PET and PVC sinking, with density higher than water, tended to increase after biofilm formation. Thereafter, the settling velocity of biofouled PET and PVC squares became faster than that of the virgin ones. In summary, our study suggested that biofouling does affect the sinking of MPs in fresh water and consequently influences the transport behavior and the distribution characteristics of MPs in freshwater environments, and this issue deserves more scientific attention., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Tire wear particles (TWP), as the significant proportion of microplastics (MPs), has adsorbed much attention due to its widespread presence in aquatic ecosystem. However, compared with traditional MPs, few studies have investigated the interaction between TWP and coexisting contaminants. The adsorption-desorption behavior of chlortetracycline (CTC) and amoxicillin (AMX) by original and aged TWP was studied, and polyethylene (PE) was studied for comparison. After aging, small holes and cracks were produced on the surfaces of the TWP and PE. Meanwhile, the specific surface areas (S BET ) of TWP and PE increased, but the aged TWP had a larger S BET than the aged PE, which indicated that TWP was more likely to degrade than PE. The adsorption kinetics results showed that the adsorption of CTC and AMX by TWP and PE conformed to the pseudo-second-order model. The adsorption isotherm results showed that the Freundlich model could describe the adsorption isotherm data of TWP and PE. The adsorption capacity of antibiotics by TWP increased by 1.13-23.40 times, and by 1.08-14.24 times on PE, after aging. Desorption experiments showed that the desorption amount of antibiotics on TWP and PE in simulated gastric fluid was greater than that in ultrapure water. The desorption amount and rate of CTC and AMX from TWP were higher than those of PE, indicating that TWP might be more harmful to the aquatic environment and organisms. These findings indicated that, compared with PE, TWP might have stronger carrier effects on antibiotics, which might pose more serious potential risks to the aquatic environment and organisms, especially considering the effects of the aging process. This study would expand the research on environmental risk of MPs and contribute to providing new insights into the evaluation of tire material particles., Competing Interests: Declaration of competing interest There are no conflicts of interest to declare., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The application of nanosized zerovalent iron (nZVI) for reductive immobilization of selenite (Se(IV)) or selenate (Se(VI)) alone has been extensively investigated. However, as the predominant species, Se(IV) and Se(VI) usually coexist in the environment. Thus, it is essential to remove both species simultaneously in the solution by nZVI. Negligible Se(VI) removal (∼7%) by nZVI was observed in the absence of Se(IV). In contrast, the Se(VI) was completely removed in the presence of Se(IV), and the removal rate and electron selectivity of Se(VI) increased from 0.12 ± 0.01 to 0.29 ± 0.02 h -1 and from 1% to 4.5%, respectively, as the Se(IV) concentration increased from 0.05 to 0.20 mM. Se(IV) was rapidly removed by nZVI, and Se(VI) exerted minor influence on Se(IV) removal. Se(IV) promoted the generation of corrosion products that were mainly composed of magnetite (26%) and lepidocrocite (67%) based on the Fe K-edge XANES spectra and k 3 -weighted EXAFS analysis. Fe(II) released during the Se(IV) reduction was not the main reductant for Se(VI) but accelerated the transformation of F(0) to magnetite and lepidocrocite. The formation of lepidocrocite contributed to the enrichment of Se(VI) on the nZVI surface, and magnetite promoted electron transfer from Fe(0) to Se(VI). This study demonstrated that Se(IV) acted as an oxidant to activate nZVI, thus improving the reactivity of nZVI toward Se(VI), which displays a potential application of nZVI in the remediation of Se(IV)- and Se(VI)-containing water.

In recent years, tire wear particles (TWP), as the significant proportion of microplastics (MPs), has adsorbed much attention due to its widespread presence in aquatic ecosystem. Compared with typical MPs, TWP exists significant differences in composition, additives, characteristics and so on. With TWP and polypropylene (PP) as target MPs, Cd 2+ and Pb 2+ as target pollutants, the adsorption-desorption characteristics of heavy metal ions on original and aged MPs were studied. Compare with the PP, the S BET of TWP increased more significantly after the UV ageing process. Meanwhile, the zeta potential of TWP increased from -8.01 to -14.6 mV and PP from -5.36 to -9.52 mV, and the surface of the TWP were more negatively-charged. In addition, the hydrophilicity of MPs enhanced due to the increased oxygen-containing functional groups after ageing process. Compared with PP, the physicochemical properties of TWP changed more obviously during UV ageing processes. The adsorption results showed that the pseudo-second-order model could better describe the adsorption processes of Cd 2+ and Pb 2+ on MPs. Meanwhile, the orders of adsorption capacity of MPs for Cd 2+ and Pb 2+ were aged TWP > aged PP > original TWP > original PP. The phenomenon of adsorption confirmed that TWP had better vector effects for heavy metal ions than PP, and the ageing processes could enhance the adsorption capacity of MPs. Moreover, the desorption results demonstrated that, compared with PP, the TWP (with higher adsorption capacity) also had the better desorption capacity for heavy metal ions in simulated gastric fluid. Compared with PP, the TWP might cause a more serious hazard to aquatic environment and organisms. These investigations would contribute to assessing the potential environmental and biological risk of TWP, especially considering the effect of the ageing process., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The effects of algae on the removal of contaminant by iron sulfide (FeS) are still unknown. Chlorella vulgaris (CV), a remarkable algal specie, was used to prepare the CV-supported FeS (CV-FeS) and to investigate the role that CV plays in the removal of a heavy metal (i.e., hexavalent chromium (Cr(VI)) by FeS. The stabilized effect from algal extracellular polymeric substance (EPS) enhanced the reactivity of FeS due to the decrease of FeS aggregation, thus increasing Cr(VI) removal rate from 0.21 min -1 to 0.79 min -1 . Furthermore, the strong buffering induced by the algal functional groups could effectively prevent the solution pH from increasing, which improved Cr(VI) removal because acidic solution facilitated Cr(VI) reduction by FeS. However, the complexing capacity from algal EPS made Fe(II) unavailable for Cr(VI) reduction, which led to 35% decrease of Cr(VI) removal. The Fe(II) was oxidized to α-FeOOH by Cr(VI) in the absence of CV, while the unreacted Fe(II) was detected as in the form of Fe(OH) 2 in CV-FeS. Cr(VI) was reduced to Cr(III) and S(-II) was oxidized to elemental sulfur (S 8 ) regardless of the CV. This work showed the different roles of algae in the removal of Cr(VI) by FeS and provided value information for the application of FeS in the polluted algae-containing water system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Application of sewage sludge biochar as an adsorbent for pollutant removal has obtained special attention due to their low cost and surface functionality. In this research, sludge-tire composite biochar (STB) was successfully prepared through co-pyrolysis at 300, 500 and 700 °C, respectively. Cadmium (Cd) and tetracycline (TC) were selected as the target pollutant. The results indicated that STB has the highest surface area (49.71 m 2 /g), more inorganic minerals (Kaolinite) as well as relatively stable physicochemical properties with 10% tire particles (TP) at 700 °C. The adsorption results indicated that the pseudo-second-order equation and Langmuir isotherm model could better describe the adsorption of Cd 2+ and TC by STB. The maximum adsorption capacity of Cd 2+ and TC was 50.25 mg/g and 90.09 mg/g, respectively. The main mechanism of the adsorption process of STB for Cd mainly involves anion binding adsorption and ion exchange. The main mechanism of the adsorption process of STB for TC mainly involves complexation and cation exchange. The present study could set a scientific foundation for further research on the recycle of sewage sludge and tires.

The adsorption behaviors of methylene blue (MB) on microalga residue powder (MRP) and biochars derived from microalga residue (MRB) produced at different pyrolytic temperatures were compared. Six biochars were prepared from residual Chlorella sp. and Spirulina sp. at different pyrolytic temperatures in the range of 200-550 °C. The adsorption kinetics, isotherms, thermodynamics, and the effect of pH were studied, and chemical analyses of MB-loaded MRP and MRB were conducted using SEM, FTIR, and XPS techniques. The results found that the pseudo-second-order, Elovich, and Freundlich models could effectively describe the MB adsorption process on MRP and MRB. The thermodynamic results confirmed that the adsorption processes were spontaneous and endothermic. Further, MRP showed an excellent adsorption ability on MB through electrostatic interaction, complexation with oxygen/nitrogen-containing functional groups and π-π interaction. However, massive oxygen-containing functional groups after pyrolysis were lost, leading to a significant decrease in the adsorption capacity of MRB on MB. This phenomenon was further observed with increasing pyrolytic temperature. Overall, this study demonstrated that microalga residue performed better for MB removal compared with their pyrolyzed analogs. Graphical abstract.

Concerns are growing about the increasing amounts of microplastics (MPs) and their ecological impacts, especially the influences of "plastisphere" in the freshwater ecosystems. Although the microbial structure and composition of biofilms are investigated, knowledge of their microbial functions remains limited. Herein, we investigated the functional diversity of carbon metabolism in biofilms colonizing one inert (glass) and two MPs as polyvinyl chloride (PVC) and polyethylene terephthalate (PET) substrates incubated for 44 days in situ in the Niushoushan River, the Qinhuai River, and Donghu Lake. 2D confocal laser scanning microscopy images visualized distinct micro-structures and biofilm compositions on three substrates. BIOLOG ECO microplates indicated variation on carbon utilization capacities of biofilms of inert and MPs in three freshwater ecosystems. Biofilms on PET showed lower capacities and carbon metabolism rates than those on glass and PVC, indicating the presence of substrate-specific functional diversity. The Shannon-Wiener diversity, Simpson diversity and Shannon evenness indices for the Niushoushan River and Donghu Lake were ordered as glass > PVC > PET. Besides to MPs-specific factors, environmental factors including nutrient (i.e., TN and TP) and turbidity largely shaped biofilm carbon metabolism. Overall findings demonstrated that as specific niches, MPs influenced microbial-mediated carbon cycling in the freshwater ecosystems and MPs-promoted microbial communities posed ecological significance., (Copyright © 2020 Elsevier B.V. All rights reserved.)

To assess the potential vector effects of degradable MPs (microplastics) on the coexisting pollutant, the adsorption-desorption behaviors of tetracycline (TC) and ciprofloxacin (CIP) by the original and aged polylactic acid (PLA) was investigated. Compared with PVC, the physicochemical properties of PLA changed more observably during the UV ageing. The original smooth surface of PLA appeared holes and cracks, and the S BET of PLA increased a 2.66-fold after the aging experiments. During the ageing processes, the hydrophily of aged MPs was also enhanced due to the increase of oxygen-containing functional groups. And the zeta potential of PLA decreased from -7.79 to -13.51 mV and PVC from -4.96 to -8.34 mV, respectively. In adsorption experiment, both the original and aged PLA showed better vector effects for antibiotics than PVC. The ageing factor increased the adsorption capacity of antibiotics on PLA 1.18-2.19 times. The desorption experiments showed that the desorption amount of antibiotics on MPs in simulated intestinal fluid was greater than that in Milli-Q water. On this basis, the desorption capacity of antibiotics with PLA was better than that of PVC, which proved that the potential negative impact of PLA on the aquatic environment and organisms might be more serious., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Parameters such as the settling rate, aggregation rate, and collision frequency in predictive models used to describe the fate of nanoparticles (NPs) are very important for the risk assessment of NPs in the environment. In this study, CeO 2 NPs were chosen as the model particles to investigate such parameters through aggregation-settling experiments under environmentally relevant conditions. The results indicate that natural colloids (Ncs) have no effect on the settling of NPs in seawaters, whereas they stabilize the NPs at a low initial particle concentration and promote the heteroaggregation of NPs at a high initial particle concentration in lake waters. In all cases, a suspended sediment absorbs the NPs and Ncs as mixed aggregates, resulting in a rapid settling. Furthermore, the calculation results of the model indicate that the shear force increases the collision frequency of the NPs by 4-5 orders of magnitude higher than that in quiescent waters. However, the break-up effect by the shear force is more obvious, namely, the shear force hinders the aggregation of NPs in natural waters, instead of promoting aggregation. Remarkably, a negative value of the dis-heteroaggregation rate based on the combined von Smoluchowski-Stokes equation can reflect the hindering effect on the aggregation process. The results of this study will provide scientific and accurate guidance for the parameter selection in the existing prediction model and contribute to a prediction of the fate and transport of NPs in the environment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Microplastics (MPs) can disintegrate into smaller sized microplastics and even nanoplastics (NPs). The toxicity of nanoplastics and microplastics on freshwater organisms have been well explored recently, however, very little is known about the potential impacts of NPs on freshwater biofilms, which are essential for primary production and nutrient cycling in aquatic ecosystems. In this study, we studied the acute effects (3 h of exposure) of polystyrene beads (PS, with diameter range from 100 nm to 9 μm) on five biological endpoints targeting community and ecosystem-level processes in biofilms: chlorophyll a, photosynthetic yield, and three extracellular enzyme activities. The results showed that the large size PS beads (500 nm, 1 μm, and 9 μm) exhibited negligible effects on the determined biological endpoints in biofilms within the range of concentrations (5-100 mg/L) in this study. However, high concentration of PS beads (100 nm, 100 mg/L) significantly decreased the content of chlorophyll a, and the functional enzyme activities of β-glucosidase and leucine aminopeptidase, suggesting negative effects on the carbon and nitrogen cycling of freshwater biofilms. Moreover, the influences of PS NPs (100 nm) on biofilms strongly depended on the surface modification of PS particles, with the positively charged PS NPs (amide-modified) exhibiting the highest toxicity to biofilms. The excess generation of reactive oxygen species (ROS) in this study indicated oxidative stress induced by PS NPs, which might lead to the observed nano-toxic effects on biofilms. In response, the antioxidant activity of biofilm was enhanced as indicated by the increased total antioxidant capacity (T-AOC). Overall, our findings highlight nanoplastics have potential to disrupt the basic ecological functions of biofilms in aquatic environments., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The widespread application of commercial TiO 2 NPs inevitably leads to their release into environmental waters through various ways. TiO 2 NPs released into water might be absorbed by and react with periphytic biofilms, which are a kind of aquatic environmental media of important ecological significance, and influence the physiological activity and ecological function of periphytic biofilms. This study investigated the effects of exposure to 1 mg/L and 5 mg/L of TiO 2 NPs on periphytic biofilms cultured indoors. After a 10-day exposure to TiO 2 NPs, the growth (measured by chlorophyll-a content) of microalgal community was inhibited greatly (more than 60%); however, the primary production (indicated by quantum yield) of periphytic biofilms maintained changeless. As for bacteria, TiO 2 NP-exposure increased the bacterial diversity and altered the composition structure. Significant changes were observed in the bacterial communities at the class level, mainly including Alphaproteobacteria, Gammaproteobacteria, Cytophagia, Flavobacteriia, Sphingobacteriia, Synechococcophycideae and Oscillatoriophycideae. The enhancement of metabolic activities (the production of extracellular polymeric substances, especially proteins content increased by 48.51%) of periphytic biofilms was a resistance mechanism to toxicity of NPs. As for extracellular enzyme activities of periphytic biofilms, alkaline phosphatase activity was inhibited (22.43%) after exposed to 5 mg/L of TiO 2 NPs, which posed a threat to phosphorus metabolism of periphytic biofilms. Overall, this study demonstrated that 1 mg/L and 5 mg/L of TiO 2 NPs negatively influenced physiological activities and ecological functions of periphytic biofilms, highlighting that the ecological risks of TiO 2 NPs should be paid attention to., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, we investigated the effects of copper oxide (CuO) NPs on freshwater sediment biofilms in terms of the functional properties and microbial community structure. Biofilms were incubated in microcosms and CuO NPs (1 mg/L uncoated and humic-acid-coated) were exposed with Cu 2+ (Cu(NO 3 ) 2 ) as the positive control. As determined from DO (dissolved oxygen) microelectrodes measurements, a high-DO region emerged inside the biofilms after 5-day exposure to CuO NPs compared with those before NP additions, which suggested CuO NPs inhibit the oxygen respiration activity. These results were consistent with the decreased heterotrophic respiration. CuO NPs significantly altered the bacterial community composition and decreased the abundances of Anaerolineaceae, Acidobacteria, Aminicenantes, and Anaerolinea. Functional analysis from PICRUSt (Phylogenetic Investigation of Communities by Reconstruction of Unobserved States)-predicted metagenomes indicated that bacterial genera depleted by CuO NP treatments were related to carbohydrate and glycan biosynthesis and metabolism, and biosynthesis of other secondary metabolites. These functional profiles combined with the decreased activities of extracellular enzymes, β-glucosidase (GLU) and l-leucine aminopeptidase (LAP), suggested that the introduction of CuO NPs exhibit negative effects on the biogeochemical processes and the cycling of carbon and nitrogen in biofilm systems. Whereas these toxic effects of CuO NPs could be mitigated when the aquatic environment is enriched with natural organic matters such as humic acid., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Microplastics are frequently detected in freshwater environments, serving as a new factitious substrate for colonization of biofilm-forming microorganisms. Distinct microbial assemblages between microplastics and surrounding waters have been well documented; however, there is insufficient knowledge regarding biofilm colonization of plastic and non-plastic substrates, despite the fact that microbial communities generally aggregate on natural solid surfaces. In this study, the effects of substrate type on microbial communities were evaluated by incubation of biofilms on microplastic substrates (polyethylene and polypropylene) and natural substrates (cobblestone and wood) for 21 days under controlled conditions. Results from high-throughput sequencing of 16S rRNA revealed that the alpha diversity (richness, evenness, and diversity) was lower in the microplastic-associated communities than in those on the natural substrates, indicating substrate-type-coupled species sorting. Distinct community structure and biofilm composition were observed between these two substrate types. Significantly higher abundances of Pirellulaceae, Phycisphaerales, Cyclobacteriaceae, and Roseococcus were observed on the microplastic substrates compared with the natural substrates. Simultaneously, the functional profiles (KEGG) predicted by Tax4Fun showed that the pathways of amino acid metabolism and metabolism of cofactors and vitamins were increased in biofilms on the microplastic substrates. The findings illustrate that microplastic acts as a distinct microbial habitat (compared with natural substrates) that could not only change the community structure but also affect microbial functions, potentially impacting the ecological functions of microbial communities in aquatic ecosystems., (Copyright © 2018 Elsevier B.V. All rights reserved.)

With the accelerated application of copper oxide (CuO) and zinc oxide (ZnO) nanoparticles (NPs) in commercial products, concerns about the potential impacts on the environment have been growing. Environmental behaviors of NPs are expected to significantly influence their fate and ecological risk in the aquatic environment. In this study, the environmental behaviors of two metallic NPs (CuO and ZnO NPs), including aggregation, sedimentation, and dissolution, were systematically evaluated in five representative waters (pool water, lake water, rainwater, tap water, and wastewater) with varying properties. Remarkable aggregation, sedimentation, and dissolution were observed for both metallic NPs, among which ZnO NPs exhibited greater influence. CuO (ZnO) NPs aggregated to 400 (500) nm, 500 (900) nm, and 800 (1500) nm in lake water, wastewater, and tap water, respectively. The sedimentation rates of CuO and ZnO NPs in the five waters were ranked as tap water > wastewater > lake water > pool water > rainwater. The dissolution of CuO and ZnO NPs in waters follows a first-order reaction rate model and is affected by ionic type, ionic strength (IS), and NOM (natural organic matter) concentrations. Redundancy analysis (RDA) indicated that the aggregation and sedimentation of NPs have a strong correlation, insofar as the sedimentation rates increase with increasing aggregation rates. The aggregation and dissolution of NPs have a negative correlation, insofar as the dissolution rates reduce with increasing aggregation rates. The aggregation, sedimentation, and dissolution of NPs can be influenced by ionic types, IS, and TOC in waters, among which, TOC may the dominant factor.

Spatial and seasonal variations of particulate phosphorus (PP) in a large shallow, eutrophic Lake Taihu with different ecotypes (including a phytoplankton-dominated zone, lake center zone, estuary zone and macrophyte-dominated zone) were investigated. The results showed that particulate organic phosphorus (POP) was the dominant form of PP (>88.0%). The concentration of POP showed higher levels in the bloom-sensitive northwestern zone (phytoplankton-dominated zone and estuary zone) during warm seasons, phytoplankton blooms and input of exogenous particulate matter were the main sources of POP in the lake water. Based on 31 P nuclear magnetic resonance ( 31 P NMR) analysis, orthophosphate (Ortho-P) was the dominant molecular species of PP and positively correlated with soluble reactive phosphorus (SRP) ( p < 0.01). This suggested that the release of Ortho-P from suspended particulate matter (SPM) was the main source of SRP in the lake water. Pyrophosphate (Pyro-P), which is regarded as a highly labile species of P compounds, represented a large fraction of PP, and its significant positive correlations with chlorophyll a (Chl a ), indicated that the concentration of Pyro-P could be used as an important indicator for the degree of eutrophication of Lake Taihu. These results proved that PP in lake water was a significant factor supporting lake eutrophication and must be controlled.

With the rapid development of CeO 2 nanoparticles (NPs), the released CeO 2 NPs entering into wastewater treatment plants might bring the challenges for sludge pumping and mixing. In this study, we firstly elucidated the rheological behavior of 4.0 wt% sludge at various concentrations of CeO 2 NPs. With the increase of CeO 2 NPs to 5 mg/L, the shear stress at any given shear rate was reduced and the limiting viscosity was also decreased, indicating the sludge became more flowability. The dynamic sweep tests further demonstrated the decreased elastic behavior and weakened internal structure in response to low concentrations of CeO 2 NPs (≤ 5 mg/L). However, 20 mg/L CeO 2 NPs had negative effects on the rheological evolution of sludge, namely, better solid-like property and higher elastic structure. These results were mainly attributed to the combination of the decreased β-D-glucopyranose polysaccharides which support the rigid structure of sludge and the dramatically increased protein content (especially in 20 mg/L CeO 2 NPs). These results can potentially provide novel information for the efficient design of sludge treatment when coped with CeO 2 NPs. Graphical abstract ᅟ.

The widespread use of commercial silver nanoparticles (Ag NPs) inevitably results in their increased release into natural waters and subsequent deposition in sediments, requiring the environmental impact of such deposition to be closely investigated. Hence, the effects of Ag NPs, polyvinylpyrrolidone (PVP)-Ag NPs, and sliver sulfide nanoparticles (Ag 2 S NPs) on denitrification-induced gas production (N 2 O and 15 N-N 2 ), and denitrifying microbes in freshwater sediments were investigated. Slurry experiments (8 h) combined with a 15 NO 3 - addition technique were performed to determine the gaseous production. The abundance of relative functional genes (nirK, nirS and nosZ) and the composition of functional community were determined through RT-PCR and high-throughput sequencing, respectively. The obtained results showed that the toxicity of NPs on denitrification depended on their type (Ag +  > Ag NPs > PVP-Ag NPs > Ag 2 S NPs) and concentration, e.g., all 1 mg/L NPs exhibited no effects on denitrification, whereas evident hormesis effect-induced acceleration was observed in the case of Ag + . Conversely, 10 mg/L Ag + and Ag NPs significantly inhibited the release rates of N 2 O and N 2 by decreasing the abundance of functional genes (nirK and/or nirS) and the predominant bacteria Paracoccus. PVP-Ag and Ag 2 S NPs had no effects on N 2 release rates and the composition of denitrifiers, however, inhibited the emission of N 2 O (by reducing the abundance of nirK), suggesting that normal denitrification-induced N 2 formation in sediments could still be sustained when the N 2 O production decrease lied within a certain range. Further, the inhibiting ability of Ag-containing NPs was caused by their intrinsic nanotoxicity to functional microbes rather than by the general toxicity of Ag + . Besides, Ag 2 S NPs (as a main detoxification form of AgNPs) were revealed to be intrinsically nanotoxic to denitrifiers, albeit showing the lowest inhibitory effect among the three tested NPs. Thus, this study demonstrated that the inhibitory effect of Ag-containing NPs on denitrification in sediments depends on their morphology and type, implying that the stability and toxicity of Ag-containing NPs should be considered with caution., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The behaviors of nanoparticles rely on the aqueous condition such as natural organic matter (NOM). Therefore the presence of NOM would influence the interaction of nanoparticles with other substances possibly. Here, microcystin-LR (MC-LR) adsorption on iron oxide nanoparticles (IONPs) was studied in an aqueous solution with different types of NOM, including extracellular polymeric substances (EPS) from cyanobacteria and alginic acid sodium salt (AASS) from brown algae. Results revealed that EPS played an important role in stabilizing IONPs and in the toxin adsorption efficiency. The stability of IONPs was heavily depended on the concentration and type of NOM, which can affect the surface charge of IONPs significantly in solution. The enhanced stability of IONPs was due to the electrostatic interactions. Adsorption kinetics and isotherm studies confirmed that NOM can affect the IONPs' adsorption efficiency, and pseudo-second-order kinetics better explained this process. The removal efficiency for MC-LR decreased in the presence of NOM (Control > EPS-M1 > AASS > EPS-M9), indicating that NOM and MC-LR compete for limited adsorption sites. The presence of NOM in a eutrophic environment stabilized the IONPs while inhibiting the MC-LR removal efficiency. This investigation emphasized the negative effect of cyanobacterial EPS on the removal of microcystins when using magnetic separation technology. And this results could also be used to model the transportation of iron minerals carrying toxic substances in aqueous environment., (Copyright © 2017. Published by Elsevier Inc.)

This study investigated the transport and long-term release of stabilized poly vinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) in a quartz sand column with various sand grain sizes (0.3-0.5 μm, 0.5-1.0 μm, 1.0-2.0 μm), input concentrations of PVP-AgNP solution (1, 5, 15, 25 mg/L), and flow rates corresponding to a filter velocities (1.0, 1.5, 2.0, 2.5 mL/min-0.14, 0.21, 0.28, 0.35 cm/min) by determining breakthrough curves, retention profiles, and long-term release curves. Breakthrough curves and retention profiles were simulated by a mathematical model based on the advection dispersion equation coupled with second-order kinetics. The increased transport of PVP-AgNPs in quartz sand occurred with increased grain sizes and reduced input concentrations, and the transport can be predicted by the colloid filtration theory and DLVO theory. The long-term (one week) release amounts of retained PVP-AgNPs were 42.78%, 31.45%, and 10.95% in the fine, medium, and coarse sand columns, respectively, and were 34.70%, 40.79%, 47.24%, and 57.32% at flow rates of 0.0363, 0.0436, 0.0545, and 0.0726 mL/min, respectively. The released quantity of retained PVP-AgNPs decreased as the sand grain size increased. This phenomenon is opposite with the trend of increased transport of PVP-AgNPs with increased grain size in the transport test, which most likely because colloidal filtration regulates the transport process and adsorption (and desorption) dominates the release process. Increasing the flow rate increased the shear force on the particles, which improved the release of PVP-AgNPs. The results of the release tests further verified our previous published studies showing that the long-term release of retained PVP-AgNPs in the quartz sand was mostly in the form of released nanoparticles rather than ions. The results of this study indicated that sand grain size, input concentration, and flow rate have a prominent influence on the transport and long-term release behavior of PVP-AgNPs in saturated quartz sand., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The increased use of silver nanoparticles (AgNPs) will inevitably result in the release of these particles into aquatic environments, with sediments as a substantial sink. However, we do not know whether AgNPs present potential impacts in sediment functioning. In this study, a microcosm approach was constructed, and the potential impacts of AgNPs and PVP-coated AgNPs on oxygen consumption in freshwater sediments (collected from Taihu Lake) were determined using oxygen microelectrodes. To our knowledge, this is the first time that microelectrodes have been used to estimate the impacts of AgNPs in sediments. The steady-state oxygen microprofiles showed that environmental relevant concentration (1 mg/L nano-Ag) did not lead to an apparent change in the oxygen consumption rates of benthic microbial communities in sediment. The addition of 10 mg/L uncoated AgNPs resulted in remarkable differences in the oxygen concentration profiles within 4-5 h and significantly inhibited the oxygen consumption of benthic microbial communities in the upper sediment layer (∼1 mm) after 100 h. Simultaneously, an increase of oxygen consumption in sediment lower zones was observed. These results may suggest that aerobic microorganisms in the upper layer of the sediment reduced metabolic activity to avoid the toxic stress from AgNPs. Concomitantly, facultative aerobes below the metabolically active upper layer switched from fermentation or anaerobic respiration to aerobic respiration as oxygen bioavailability increased in the lower zones of the sediment. In addition, PVP coating reduced the nanotoxicity of AgNPs in benthic microorganisms due to the decreased dissolution of AgNPs in the filtered overlying water, a phenomenon that merits further investigation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The co-presence of perfluorooctane sulfonate (PFOS) and phosphate in wastewater of various industries has been detected. Removing PFOS and phosphate simultaneously before discharging sewage into natural water can decrease effectively the environmental risk caused by the combined pollution of PFOS and phosphate. In this study, laboratory batch experiments were conducted for investigating the co-adsorption of PFOS and phosphate on boehmite and the influences of temperature, phosphate initial concentration and pH on the co-adsorption. The adsorption thermodynamics and kinetics of PFOS and phosphate on boehmite were also investigated completely and systematically. The results showed that lower temperature favored the co-adsorptions of PFOS and phosphate. The adsorption of PFOS and phosphate on boehmite agreed well with the Langmuir isotherm and the adsorption parameters of thermodynamics are ΔH=-16.9 and -20.0kJmol -1 (PFOS and phosphate), ΔS=-5.69 and -7.63Jmol -1 K -1 (PFOS and phosphate) and ΔG <0 (PFOS and phosphate). It demonstrated that the co-adsorption of PFOS and phosphate on boehmite is a spontaneously exothermic process. Moreover, the co-adsorption process can be described well by a pseudo-second-order kinetic model. With increasing phosphate initial concentration, more phosphate could be adsorbed on boehmite, while the adsorption of PFOS decreased at phosphate initial concentration of less than 30mgL -1 and increased at that of larger than 30mgL -1 . In the co-adsorption process, the adsorption amount of PFOS decreased with pH increasing, but that of phosphate changed little., (Copyright © 2016. Published by Elsevier Inc.)

Extracellular polymeric substances (EPS) are key components of the cyanobacterium Microcystis aeruginosa and play an important role in cyanobacteria blooms formation. Here, we analyzed the effects of 48-h exposure to nanosized CeO 2 (n-CeO 2 ), CuO (n-CuO), and ZnO (n-ZnO) on the production and composition of EPS of M. aeruginosa. Toxicity experiments revealed that soluble nanoparticles (NPs) (n-ZnO, n-CuO) demonstrated higher toxicity to cells and caused membrane damage. The production of LB-EPS increased by 34.48, 20.09, and 46.33 %, and TB-EPS increased by -5.78, 22.3, and -2.67 % in the presence of n-CeO 2 , n-CuO, and n-ZnO NPs, respectively, and polysaccharides are the main incremental portion compared with protein and humic acids. Three-dimensional excitation-emission fluorescence spectra revealed the enhancement of fulvic-humic-like and disappearance of tyrosine aromatic substances in TB-EPS compared with the slight changes observed in LB-EPS. Fourier-transform infrared spectroscopy illustrated the susceptibility of -NH 2 and double-bonded carbon and oxygen in amides to three types of NPs. These results improve our understanding of the potential influence of NPs on the aggregation behaviors of cyanobacteria and formation process of cyanobacteria blooms. Graphical abstract ᅟ.

The effects of water transfer projects on water channels and the receiving water involved need to be understood. In this research, the compositions and particle size distributions of surface sediment and the Cd, Cr, Cu, Ni, Pb, and Zn contents and distributions in the sediment along a water transfer route from the Wangyu River to Taihu Lake, China, were studied. The correlative relationship between the grain size trend and heavy metal content distribution suggested that heavy metals in Wangyu River sediment have affected the heavy metal contents of Taihu Lake sediment through silt and clay migrating in the transferred water. Enrichment factors and potential ecological risk values were calculated. Low levels of potential ecological risks are posed at 20 sampling sites in Taihu Lake, but higher-to-serious risks (potential ecological risk values >275) are posed at all Wangyu River sites. Toxicity of heavy metals (Cd, Cu, Zn, and Ni) in the Wangyu River sediments is more serious than those in the Taihu Lake, but is similar to the entrance of Gonghu Bay. Multivariate statistical analyses (Pearson correlation, cluster, and factor analyses) suggested heavy metals in the study area have many sources, and the relationships between particle migration and heavy metal contents indicated transferring water are likely to lead to adverse ecological risks being posed in Taihu Lake.

Phosphorus (P) plays a critical role in algal growth; therefore, a better understanding of P availability is essential to control harmful algal blooms. Three algae species, Microcystis aeruginosa, Chlorella pyrenoidosa, and Pseudokirchneriella subcapitata, were mono-cultured and co-cultured on three types of P substrates, dissolved inorganic P (DIP), phosphomonoesters glucose-6-phosphate (G-6-P) and β-glycerol phosphate (β-glycerol-P), and phosphonate (glyphosate), to explore their growth and P utilization. All three species could utilize dissolved organic P (DOP) to sustain their growth, whereas DIP was their preferred P substrate in both culture types. Algae could regulate the P uptake capacity under different P conditions, and the added P could be rapidly accumulated at the beginning of the culture and slowly utilized during the subsequent life cycle. M. aeruginosa exhibited wider P selectivity and could utilize all three P substrates, whereas the other two species could only use phosphomonoester (G-6-P and β-glycerol-P) in the mono-cultures. However, in the co-cultures, the relative bioavailability of DOP for M. aeruginosa and C. pyrenoidosa was enhanced, and M. aeruginosa might contribute to the growth of C. pyrenoidosa and P. subcapitata when fed with glyphosate. The three species showed an intrinsic ability to produce alkaline phosphatase (AP), and AP activity (APA) was regulated by Pi stress. However, high APA did not necessarily lead to high Pi release and algal growth on unfavorable substrates. Although M. aeruginosa was not superior in growth rate in the mono-cultures, it showed a better P accumulation ability and maintained stable growth on different P substrates. Moreover, it was a good competitor, suppressing the thriving growth of the other species in co-cultures. Overall, the findings indicated the strategic flexibility of P utilization by algae and the strong competitive ability of M. aeruginosa in Pi-limited and DOP-enriched natural waters., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The internal loading of P is reported to be the main factor initiating algal blooms. However, there are only a few reports on the dynamic variation of labile P in the sediment and overlying water during the decomposition of algal. In addition, the widely perceived relationship between labile P and Fe was not supported by in situ obtained values in freshwater. Consequently, the in situ simultaneous measurement of diffusion gradients in thin-film techniques (DGT) was applied on a large scale to detect the mechanisms of labile P and Fe in a typical shallow lake (Lake Hongze). The newly developed ZrO-DGT and ZrO-Chelex DGT were combined to obtain the concentration of labile P and Fe. Results showed that decomposition of algal might be the main contributor for the concentration dots and peaks of labile P in sediment profiles, as well as for the high values on the horizontal heterogeneity index of labile P at the depth of 0-30 mm of the sediment. Moreover, there existed significant difference between the apparent diffusion fluxes of labile P and Fe across the sediment-water interface which obtained from June sampling and October sampling. The results of apparent diffusion flux in two periods indicated the sediments changed from "sink" to "source" for labile P, especially at Sites 4-8, 10, 13-14, and 18. However, the role of the labile Fe has no significantly variation in the values of the diffusion flux. This phenomenon also contributed to the poor relationship between labile P and Fe in the sediment which obtained from the October sampling. Accordingly, we conclude that algal decomposition might be essential for internal loading of P in this aquatic ecosystem, and that also be the reason for vicious circle of algal occurrence in the following year in the center of Lake Hongze., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The effects of CeO 2 nanoparticles (CeO 2 NPs) on a sequencing batch biofilm reactor (SBBR) with established biological phosphorus (P) removal were investigated from the processes of anaerobic P release and aerobic P uptake. At low concentration (0.1mg/L), no significant impact was observed on total phosphorus (TP) removal after operating for 8h. However, at a concentration of 20mg/L, TP removal efficiency decreased from 83.68% to 55.88% and 16.76% when the CeO 2 NPs were added at the beginning of the anaerobic and aerobic periods, respectively. Further studies illustrated that the inhibition of the specific P release rate was caused by the reversible states of Ce 3+ and Ce 4+ , which inhibited the activity of exopolyphosphatase (PPX) and transformation of poly-β-hydoxyalkanoates (PHA) and glycogen, as well as the uptake of volatile fatty acids (VFAs). The decrease in the specific P uptake rate was mainly attributed to the significantly suppressed energy generation and decreased abundance of Burkholderia caused by excess reactive oxygen species. The removal of chemical oxygen demand (COD) was not influenced by CeO 2 NPs under aerobic conditions, due to the increased abundance of Acetobacter and Acidocella after exposure. The inhibitory effects of CeO 2 NPs with molecular oxygen were reduced after anaerobic exposure due to the enhanced particle size and the presence of Ce 3+ ., (Copyright © 2016. Published by Elsevier Inc.)

The impacts of CuO nanoparticle (NP) exposure on total nitrogen (TN) removal in a sequencing batch biofilm reactor (SBBR) as well as the effects of natural organic matter (NOM) in wastewater were studied. Short-term exposure (8 h) to 1 and 50 mg/L CuO NPs induced negligible influence on the nitrogen removal efficiency, and biofilms could recover from the slight damage caused by the prolonged exposure (45 days) to 1 mg/L CuO NPs. On the other hand, long-term exposure to 50 mg/L CuO NPs notably decreased the nitrogen removal efficiencies to 47.74 and 59.04 % in the absence and presence of bovine serum albumin (BSA), much lower than those in the control (75.43 %), mainly as the suppressed denitrification process. Analysis of key enzyme activities showed that the activities of nitrite reductase and nitrate reductase were obviously reduced with 50 mg/L CuO NP exposure. Further studies revealed that the inhibited nitrite/nitrate reductase was related to the variations of microenvironment pH and decrease of nirS and nirK by microelectrode and fluorescent quantitative polymerase chain reaction (PCR) analysis. In addition, the presence of BSA mitigated the toxicity of CuO NPs due to the enhanced particle size and Cu 2+ release, electrostatic repulsion, and surface coating of CuO NPs, which indicated that lower inhibition effects of CuO NPs in NOM-rich wastewater is of importance when evaluating the environmental risk of NPs to wastewater treatment plants.

A novel Zr oxide diffusive gradients in thin films (DGT)-based measurement technique for high-resolution imaging of labile Cr (VI) is introduced in this study. The method is based on the diphenylcarbazide coloration technique for Cr (VI) combined with computer-imaging densitometry, which provides a relation between the accumulated mass of Cr (VI) and the grayscale intensity. The Zr oxide gels show good performance in reflecting the accurate measurement of Cr (VI), independent of the effects of pH, ionic strength, and PO4(3-) concentration. Settling of the Zr-oxide gel was identified as a simple and effective method to suppress leaching of the claret-colored compound out of the gel. In addition, the optimal volume of added coloration reagent was 125 times that of the binding gel and 30min was selected as the optimal time for the chromogenic reaction. The relationship between the accumulated Cr (VI) and grayscale intensity was analyzed under the optimized conditions. The Zr oxide DGT technique could also obviously reflect the heterogeneity of sediment. Consequently, Zr oxide DGT-based coloration is certified to be a robust and suitable tool for providing effective and high-resolution information on bioavailable Cr (VI)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

To improve our understanding of the Si-related biogeochemical processes that occur in estuarine ecosystems with large subaqueous deltas (e.g., the Yangtze Estuary; YE), the speciation of Si in the surface sediments of the YE was investigated. The relationships between the different Si species and sediment bulk parameters were also discussed. Based on modified sequential extraction method, we can successfully estimate the following five sedimentary potentially mobile Si pools: weak acid leachable Si (W-Si); Si bound to organic matter (H-Si); Si coprecipitated with amorphous Fe/Al oxides (O-Si); Si coprecipitated with crystalline Fe/Al oxides (Ouv-Si), and biogenic silica (B-Si). The total potentially mobile Si pool (T-Si) ranged between 1689.31 and 5487.10 μg/g, with high values observed in deltaic mud deposits. The Si fractions were closely correlated with grain size compositions, except for O-Si. In deltaic mud deposits, efficient loss of organic matters and recycling of Fe oxides probably resulted in the amorphous or poorly crystalline Fe oxides uncoupled with the clay fractions, and thus leading to the lack of correlation between O-Si and grain size. As compared with Ouv-Si, the O-Si should possess stronger mobility, which highlights the importance of quantifying the O-Si pool in deltaic sediments.

The transport behaviors of copper oxide (CuO) NPs in wastewater matrix and their possible impacts on microbial activities of stable wastewater biofilms cultivated in a lab scale rotating biological contactor (RBC) were investigated. Significant aggregation of CuO NPs was observed in the wastewater samples, depending on their mass concentrations. Extracellular polymeric substance (EPS)-adsorbed copper accounted for a large proportion of the total copper accumulated in biofilms. The microelectrode profiles showed that a single pulse exposure to 50mg/L CuO resulted in a deeper penetration depth of oxygen in biofilms compared to the CuO NP free biofilms. The maximum oxygen consumption rate shifted to the deeper parts of biofilms, indicating that the respiration activities of bacteria in the top region of the biofilms was significantly inhibited by CuO NPs. Biofilms secreted more EPS in response to the nano-CuO stress, with higher production of proteins compared to polysaccharides., (Copyright © 2016 Elsevier Ltd. All rights reserved.)