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Plastics ranging from nano-scale to micron-scale are frequently ingested by many marine animals. These particles exhibit biotoxicity and additionally perform as vectors that convey and amass adsorbed chemicals within organisms. Meanwhile, the frequency of detection of the benzophenone-3 and ciprofloxacin can be adsorbed on plastic particles, then accumulated in bivalves, causing biotoxicity. To understand their unknown accumulative kinetics in vivo affected by different plastic sizes and toxic effect from co-exposure, several scenarios were set up in which the mode organism were exposed to 0.6 mg/L of polystyrene carrying benzophenone-3 and ciprofloxacin in three sizes (300 nm, 38 μm, and 0.6 mm). The live Asian green mussels were chosen as mode organism for exposure experiments, in which they were exposed to environments with plastics of different sizes laden with benzophenone-3 and ciprofloxacin, then depurated for 7 days. The bioaccumulation and depuration kinetics of benzophenone-3 and ciprofloxacin were measured using HPLC-MS/MS after one week of exposure and depuration. Meanwhile, their toxic effect were investigated by measuring the changes in six biomarkers (condition index, reactive oxygen species, catalase, glutathione, lipid peroxidation, cytochrome P450 and DNA damage). The bioconcentration factors in mussels under different exposure conditions were 41.48–111.75 for benzophenone-3 and 6.45 to 12.35 for ciprofloxacin. The results suggested that microplastics and nanoplastics can act as carriers to increase bioaccumulation and toxicity of adsorbates in mussels in a size-dependent manner. Overproduction of reactive oxygen species caused by microplastics and nanoplastics led to increased DNA damage, lipid peroxidation, and changes in antioxidant enzymes and non-enzymatic antioxidants during exposure. Marked disruption of antioxidant defenses and genotoxic effects in mussels during depuration indicated impaired recovery. Compared to micron-scale plastic with sizes over a hundred micrometers that had little effect on bivalve bioaccumulation and toxicity, nano-scale plastic greatly enhanced the biotoxicity effect. [Display omitted] • Bioaccumulation can be accelerated by microplastics and is significantly enhanced by nanoplastics. • Benzophenone-3 was more readily bioconcentrated and less readily eliminated. • Biotoxicity induced by nanoplastics was not completely mitigated following depuration. • Microplastics and nanoplastics disrupted antioxidant systems more than chemicals alone in mussels. [ABSTRACT FROM AUTHOR]

Arsenic (As) pollution in wetlands has emerged as a serious global concern, posing potential threat to the growth of wetland plants. Arbuscular mycorrhizal fungi (AMF) can alleviate As phytotoxicity to host plants, but their ecological functions in wetland plants under flooding conditions remain largely unknown. Thus, a pot experiment was conducted using Rhizophagus irregularis and Iris tectorum Maxim. exposed to light (15 and 30 mg/kg As) and high (75 and 100 mg/kg As) levels of As, to investigate the intrinsic mechanisms underlying the effects of mycorrhizal inoculation on plant As tolerance under flooding conditions. The mycorrhizal colonization rates ranged from 31.47 ± 3.92 % to 60.69 ± 5.58 %, which were higher than the colonization rate (29.55 ± 13.60%) before flooding. AMF significantly increased biomass of I. tectorum under light As levels, together with increased phosphorus (P) and As uptake. Moreover, expression of arsenate reductase gene RiarsC and a trace of dimethylarsenic (1.87 mg/kg in shoots) were detected in mycorrhizal plants, suggesting As transformation and detoxification by AMF exposed to light levels of As. However, under high As levels, AMF inhibited As translocation from roots to shoots, and facilitated the formation of iron plaque. The immobilized As concentrations in iron plaque of mycorrhizal plants were respectively 1133.68 ± 179.17 mg/kg and 869.11 ± 248.90 mg/kg at 75 and 100 mg/kg As addition level, both significantly higher than that in non-inoculated plants. Irrespective of As exposure levels, mycorrhizal symbiosis decreased soil As bioavailability. Overall, the study provides insights into the alleviation of As phytotoxicity in natural wetland plants through mycorrhizal symbiosis, and potentially indicates function diversity of AMF under flooding conditions and As stress, supporting the subsequent phytoremediation and restoration of As-contaminated wetlands. [Display omitted] • Arbuscular mycorrhizal fungi (AMF) survived in flooding conditions. • AMF improved plant growth and upregulated RiarsC under light As levels. • Mycorrhizal symbiosis facilitated iron plaque formation under high As levels. • Mycorrhizal inoculation decreased soil As bioavailability. [ABSTRACT FROM AUTHOR]

Understanding the sources, occurrence and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in the urban water cycle is important to protect and utilize local water resources. Concentrations of 22 target PFASs and general water quality parameters were determined monthly for a year in filtered water samples from five tributaries and three sampling stations of an urban water body. Of the 22 target PFASs, 17 PFASs were detected with a frequency >93% including PFCAs: C4-C12 perfluoroalkyl carboxylates, C4, C6, C8, and C10 perfluoroalkane sulfonates, perfluorooctane sulfonamides and perfluorooctane sulfonamide substances (FOSAMs), C10 perfluoroalkyl phosphonic acid (C10 PFPA), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and C8/C8 perfluoroalkyl phosphinic acid (C8/C8-PFPIA). The most abundant PFASs in water were PFBS (1.4–55 ng/L), PFBA (1.0–23 ng/L), PFOS (1.5–24 ng/L) and PFOA (2.0–21 ng/L). In the tributaries, PFNA concentrations ranged from 1.2 to 87.1 ng/L except in the May 2013 samples of two tributaries, which reached 520 and 260 ng/L. Total PFAS concentrations in the sediment samples ranged from 1.6 to 15 ng/g d.w. with EtFOSAA, PFDoA, PFOS and PFDA being the dominant species. Based on water and sediment data, two types of sources were inferred: one-time or intermittent point sources and continuous non-point sources. FOSAMs and PFOS released continually from non-point sources, C8/C8 PFPIA, PFDoA and PFUnA was released from point sources. The highly water soluble short-chain PFASs including PFBA, PFPeA and PFBS remained predominantly in the water column. The factors governing solution phase concentrations appear to be compound hydrophobicity and sorption to suspended particles. Correlation of the dissolved phase concentrations with precipitation data suggested stormwater was a significant source of PFBA, PFBS, PFUnA and PFDoA. Negative correlations with precipitation indicated sources feeding FOSAA and FOSA directly into the tributaries. [ABSTRACT FROM AUTHOR]

Previous studies showed the presence of multiple emerging organic contaminants (EOCs) in urban surface waters of Singapore even though there are no obvious direct wastewater discharges. In this study, we investigated the occurrence and distribution of 17 pharmaceuticals and personal care products (PPCPs) and endocrine disruptive compounds (EDCs) in a tropical urban catchment of Singapore. Monthly samples were collected from a reservoir and its 5 upstream tributaries during a 16-month period. Analysis of samples showed all sites had measurable PPCP and EDC concentrations, with caffeine (33.9–2980 ng/L), salicylic acid (5–838 ng/L), acetaminophen (< 4–485.5 ng/L), BPA (< 2–919.5 ng/L) and DEET (13–270 ng/L) being the most abundant. Marked differences in concentrations of target analytes between the reservoir and upstream tributaries were observed, and were tentatively attributed to the spatial differences in source inputs, water dilution capacity as well as natural attenuation of EOCs. Significant correlations between EOCs and conductivity, dissolved oxygen, chlorophyll a , turbidity, nutrients and cumulative precipitation were observed. These factors appeared to affect the distribution and attenuation of EOCs, depending on their physicochemical properties. Rainfall also influenced the temporal distribution of caffeine, BPA, triclosan, fipronil and DEET in the reservoir. Ecological risk assessment showed that caffeine, acetaminophen, estrone, BPA, triclosan and fipronil may warrant further survey. In particular, BPA levels exceeded the literature-based Predicted No-Effect Concentration (PNEC) value, highlighting the need for source control and/or water remediation in this urban catchment. [ABSTRACT FROM AUTHOR]

• 16 cyanobacterial metabolites were detected in a freshwater lake in Singapore. • MC-RR and CYN occurred the most frequently, both intra- and extracellularly. • MCs decreased with increases in CYN over time. • The rapid prediction of MCs and CYN was achieved by RF using easily accessible WQIs. • Chlorophyll-a and chloride were the primary predictors for MCs and CYN, respectively. Cyanobacterial blooms that produce toxins occur in freshwaters worldwide and yet, the occurrence and distribution patterns of many cyanobacterial secondary metabolites particularly in tropical regions are still not fully understood. Moreover, predictive models for these metabolites by using easily accessible water quality indicators are rarely discussed. In this study, we investigated the co-occurrence and spatiotemporal trends of 18 well-known and less-studied cyanobacterial metabolites (including [D-Asp3] microcystin-LR (DM-LR), [D-Asp3] microcystin-RR (DM-RR), microcystin-HilR (MC-HilR), microcystin-HtyR (MC-HtyR), microcystin-LA (MC-LA), microcystin-LF (MC-LF), microcystin-LR (MC-LR), microcystin-LW (MC-LW), microcystin-LY (MC-LY), microcystin-RR (MC-RR) and microcystin-WR (MC-WR), Anatoxin-a (ATX-a), homoanatoxin-a (HATX-a), cylindrospermospin (CYN), nodularin (NOD), anabaenopeptin A (AptA) and anabaenopeptin B (AptB)) in a tropical freshwater lake often plagued with blooms. Random forest (RF) models were developed to predict MCs and CYN and assess the relative importance of 22 potential predictors that determined their concentrations. The results showed that 11 MCs, CYN, ATX-a, HATX-a, AptA and AptB were found at least once in the studied water body, with MC-RR and CYN being the most frequently occurring, intracellularly and extracellularly. AptA and AptB were detected for the first time in tropical freshwaters at low concentrations. The metabolite profiles were highly variable at both temporal and spatial scales, in line with spatially different phytoplankton assemblages. Notably, MCs decreased with the increase of CYN, possibly revealing interspecific competition of cyanobacteria. The rapid RF prediction models for MCs and CYN were successfully developed using 4 identified drivers (i.e., chlorophyll-a, total carbon, rainfall and ammonium for MCs prediction; and chloride, total carbon, rainfall and nitrate for CYN prediction). The established models can help to better understand the potential relationships between cyanotoxins and environmental variables as well as provide useful information for making policy decisions. [Display omitted] [ABSTRACT FROM AUTHOR]

We developed a comprehensive integrated water quality modeling approach towards a better understanding of the fate and transport of emerging contaminants and comprehensive assessment of their potential risks in a tropical reservoir. Two representative emerging contaminants, namely Bisphenol A (BPA) and N, N-diethyltoluamide (DEET), were selected for this study. Unlike the traditional water quality modeling approach, the target emerging contaminants were modelled in four multi-compartments and coupled to a 3D-dimensional eutrophication model to investigate their interactions with other water quality state variables. First, the integrated model was calibrated and validated in four multi-compartments against an observed dataset in 2014. Subsequently, the correlation analysis between emerging contaminants and general water quality parameters were conducted. The potential ecological risks in this reservoir were also assessed via the trophic state index (TSI) and coupled to a species sensitivity distribution (SSD)-Risk Quotient (RQ) method. Finally, the model was applied to describe the dynamics of the two emerging contaminants and examine the direct and indirect influences of other environmental factors on their multi-compartment distributions in the aquatic environment. The comprehensive approach provides new insights into dynamic modeling of the fate and transport of emerging contaminants, their interactions with other state variables as well as an assessment of their potential risks in aquatic ecosystems. [ABSTRACT FROM AUTHOR]

• Low concentrations of per/polyfluoroalkyl substances induced promoted conjugation. • High concentrations of per/polyfluoroalkyl substances induced inhibited conjugation. • Promotion effect was ascribed to enhanced ROS production and membrane permeability. • High concentrations of per/polyfluoroalkyl substances lead to the shortage of ATP. • L-arginine pool depletion contributed to the inhibited plasmid conjugation. Emerging contaminants can accelerate the transmission of antibiotic resistance genes (ARGs) from environmental bacteria to human pathogens via plasmid conjugation, posing a great challenge to the public health. Although the toxic effects of per/polyfluoroalkyl substances (PFAS) as persistent organic pollutants have been understood, it is still unclear whether and how PFAS modulate the transmission of ARGs. In this study, we for the first time reported that perfluorooctanoic acid (PFOA), perfluorododecanoic acid (PFDoA) and ammonium perfluoro (2-methyl-3-oxahexanoate) (GenX) at relatively low concentrations (0.01, 0.1 mg/L) promoted the conjugative transfer of plasmid RP4 within Escherichia coli , while the plasmid conjugation was inhibited by PFOA, PFDoA and GenX at relatively high concentrations (1, 10 mg/L). The non-unidirectional conjugation result was ascribed to the co-regulation of ROS overproduction, enhanced cell membrane permeability, shortage of energy support as well as l -arginine pool depletion. Taking the well-known PFOA as an example, it significantly enhanced the conjugation frequency by 1.4 and 3.4 times at relatively low concentrations (0.01, 0.1 mg/L), respectively. Exposure to PFOA resulted in enhanced cell membrane permeability and ROS overproduction in donor cells. At high concentrations of PFOA (1, 10 mg/L), although enhanced oxidative stress and cell membrane permeability still occurred, the ATP contents in E. coli decreased, which contributed to the inhibited conjugation. Transcriptome analysis further showed that the expression levels of genes related to arginine biosynthesis (argA, argC, argF, argG, argI) and transport (artJ, artM, artQ) pathways were significantly increased. Intracellular l -arginine concentration deficiency were observed at high concentrations of PFOA. With the supplementary exogenous arginine, it was demonstrated that arginine upregulated conjugation transfer- related genes (trfAp, trbBp) and restores the cell number of transconjugants in PFOA-treated group. Therefore, the inhibited conjugation at high concentrations PFOA were attributed to the shortage of ATP and the depletion of L-arginine pool. These findings provide important insights into the effect environmental concentrations of PFAS on the conjugative transfer of ARGs, and update the regulation mechanism of plasmid conjugation, which is critical for the management of antibiotic resistance in aquatic environments. [Display omitted] [ABSTRACT FROM AUTHOR]

Microplastics (MPs) are global pollutants with heightened environmental and health concerns in recent years because of their worldwide distribution across aquatic environments, ability to load chemical contaminants and the potential for ingestion by animals, including human. In this study, three commonly used and environmentally detected plastics, i.e. polystyrene, polyethylene, polypropylene with sizes of 550, 250 and 75 μm, plus two submicron-sized polystyrene microplastics (5 and 0.5 μm) were assessed as solid adsorbents for a prevalent UV filter, benzophenone-3 (BP-3). The affinity and process of adsorption exhibited differentials among different sizes and types of MPs. Apparent desorption of BP-3 from MPs under simulated gastrointestinal conditions was not significantly enhanced, which might be due to the presence of the enzyme proteins, indicating potential risk of the contaminants carried by MPs. The desorption of BP-3 from MPs was affected by the size, type of MPs and the components of the gastrointestinal fluid. [Display omitted] • The adsorption of Benzophenone-3 (BP-3) on microplastics exhibited significant microplastics type and size differentials. • Desorption of BP-3 from microplastics under simulated human gastrointestinal conditions was assessed. • The enzyme proteins pepsin and trypsin may result in a declined apparent desorption of BP-3 from microplastics. [ABSTRACT FROM AUTHOR]

There is limited information on the occurrence and removal of artificial sweeteners (ASs) in biological wastewater treatment plants, and in particular, the contribution of sorption and biodegradation to their removal. This study investigated the fate of ASs in both the aqueous and solid phases in a water reclamation plant (WRP). All the four targeted ASs, i.e. acesulfame (ACE), sucralose (SUC), cyclamate (CYC) and saccharine (SAC), were detected in both the aqueous and solid phases of raw influent and primary effluent samples. The concentrations of CYC and SAC in secondary effluent or MBR permeate were below their method detection limits. ACE and SUC were persistent throughout the WRP, whereas CYC and SAC were completely removed in biological treatment (>99%). Experimental results showed that sorption played a minor role in the elimination of the ASs due to the relatively low sorption coefficients ( K d ), where K d < 500 L/kg. In particular, the poor removal of ACE and SUC in the WRP may be attributed to their physiochemical properties (i.e. log K ow < 0 or log D < 3.2) and chemical structures containing strong withdrawing electron functional groups in heterocyclic rings (i.e. chloride and sulfonate). [ABSTRACT FROM AUTHOR]

• Summary of source, fate, transport of ECs in the aquatic environments. • Critically reviewed the current status of ECs models from a global perspective. • Proposed an integrated modelling approach for sound management of ECs in aquatic ecosystems. • Explored future perspectives and applications of ECs modelling approach. The occurrence of emerging contaminants (ECs), such as pharmaceuticals and personal care products (PPCPs), perfluoroalkyl and polyfluoroalkyl substances (PFASs) and endocrine-disrupting chemicals (EDCs) in aquatic environments represent a major threat to water resources due to their potential risks to the ecosystem and humans even at trace levels. Mathematical modelling can be a useful tool as a comprehensive approach to study their fate and transport in natural waters. However, modelling studies of the occurrence, fate and transport of ECs in aquatic environments have generally received far less attention than the more widespread field and laboratory studies. In this study, we reviewed the current status of modelling ECs based on selected representative ECs, including their sources, fate and various mechanisms as well as their interactions with the surrounding environments in aquatic ecosystems, and explore future development and perspectives in this area. Most importantly, the principles, mathematical derivations, ongoing development and applications of various ECs models in different geographical regions are critically reviewed and discussed. The recommendations for improving data quality, monitoring planning, model development and applications were also suggested. The outcomes of this review can lay down a future framework in developing a comprehensive ECs modelling approach to help researchers and policymakers effectively manage water resources impacted by rising levels of ECs. [Display omitted] [ABSTRACT FROM AUTHOR]

• First report of cyanobacterial community structure of Tehran dams. • Detection of seven microcystin variants with the total concentration of 130.651 ng/mg of biomass dry weight and also confirming the presence of mcyE gene in the strain Phormidium sp. UTMC6001. • Detection of cylindrospermopsin and confirming the presence of cyrA gene in the strains Limnothrix sp. UTMC6006 and Cyanobium sp. UTMC6007. • Detection of anatoxin-a in the four Phormidium, Leptolyngbya, Microcoleus and Calothrix strains with no confirmation of anaC gene. • Phylogenetic analysis of indigenous toxin producers. Monitoring toxigenic cyanobacteria in freshwaters is of great importance due to the adverse health impacts on humans and aquatic organisms. Here we studied cyanobacterial occurrence and biodiversity in a drinking water reservoir in Tehran province, Iran. In total, nine different species representing three orders of Synechococcales, Oscillatoriales and Nostocales were isolated and classified into six families and seven genera ranging from 92.3% to 99.0% similarities in their partial 16S rDNA with GenBank sequences. The cultures were analyzed for cyanotoxins production by the Artemia salina bioassay, ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and also screened for the presence of marker genes involved in toxins production. Ethyl acetate extracts of three strains showed more than 50% mortality on A. salina larvae after 24 h at a concentration of 500 µg/ml. Production of at least one of the cyanotoxins, microcystin (MC), cylindrospermopsin (CYN) and anatoxin-a (ATX-a), was detected in 6 of the strains. Seven MC variants with a total concentration of 130.6 ng/mg of biomass dry weight were detected for the strain Phormidium sp. UTMC6001 and molecular screening of the mcyE gene also confirmed the presence of this biomarker in its genome. Our study also revealed the production of CYN in a novel picocyanobacterial strain Cyanobium sp. UTMC6007 at 1.0 ng/mg of biomass dry weight. Considering the limited information on freshwater toxic cyanobacteria taxonomy in the Middle East, these findings will expand our knowledge and consequently aid in development of new water management policies in future. [ABSTRACT FROM AUTHOR]

Analytical methods based on direct injection (DI) and solid phase extraction (SPE) coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC- MS/MS) were developed for the determination of anatoxin-a (ATX-a), cylindrospermopsin (CYN), and homoanatoxin-a (HATX-a) in freshwater samples impacted with cyanobacterial blooms. The presence of CYN in freshwater samples was detected and quantified based on direct injection method, while ATX-a and HATX-a could be determined by both DI and SPE-based methods. Matrix effects (ME) on the signal intensity of the cyanotoxins were systematically evaluated for both direct injection and SPE extract samples. CYN, ATX-a, and HATX-a suffered a significant suppression during UPLC-MS/MS. The selection of internal standards (ISs) for compensating/correcting the losses of target cyanotoxins during sample preparation and matrix effects in UPLC-MS/MS analyses were systematically evaluated. Acetaminophen-d 4 (an isotopically labelled acetaminophen) is a suitable internal standard for correcting the ME on the signal intensity of ATX-a and HATX-a, while the use of L-phenylalanine-d 5 or caffeine-d 9 as IS for correcting ME of these toxins was not efficient, as expected. The method detection limit (MDL) for the target cyanotoxins ranged from 0.6 to 15 ng/L, which is sensitive enough to detect the presence of these toxins in cyanobacterial bloom freshwater. The developed methods were successfully applied for routine monitoring of the occurrence of these cyanotoxins in a local water body. Monitoring results depicted that ATX-a, CYN and HATX-a were ubiquitously detected in water samples, at concentrations ranging from 70 to 24,600 ng/L. Unlabelled Image • Three algal toxins were simultaneously quantified by UPLC-MS/MS. • UPLC-MS/MS parameters for analysis of algal toxins were optimized. • Matrix effects in UPLC-MS/MS were corrected by isotope-labelled internal standards. • Anatoxin-a and cylindrospermopsin were ubiquitously detected in bloom freshwater. [ABSTRACT FROM AUTHOR]