Little information is available about effect of particle size and crystal structure of nTiO₂ on their trophic transfer. In this study, 5 nm anatase, 10 nm anatase, 100 nm anatase, 20 nm P25 (80% anatase and 20% rutile), and 25 nm rutile nTiO₂ were selected to investigate the effects of size and crystal structure on the toxicity, bioconcentration, and trophic transfer of nTiO₂ to algae and daphnia. In the exposed daphnids, metabolic pathways affected by nTiO₂ and nTiO₂-exposed algae (nTiO₂-algae) were also explored. The 96 h IC₅₀ values of algae and the 48 h LC₅₀ values of daphnia were 10.3, 18.9, 43.9, 33.6, 65.4 mg/L and 10.5, 13.2, 37.0, 28.4, 60.7 mg/L, respectively, after exposed to nTiO₂-5A, nTiO₂-10A, nTiO₂-100A, nTiO₂-P25, and nTiO₂-25R, respectively. The bioconcentration factors (BCFs) for 0.1, 1, and 10 mg/L nTiO₂ in daphnia ranged from 21,220 L/kg to 145,350 L/kg. The nTiO₂ biomagnification factors (BMFs) of daphnia fed with 1 and 10 mg/L nTiO₂-exposed algae were consistently greater than 1.0 (5.7–122). The results show that the acute toxicity, BCF, and BMF all decreased with increasing size or rutile content of nTiO₂. All types of nTiO₂ were largely accumulated in the daphnia gut and were not completely depurated within 24 h. At the molecular level, 22 Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolic pathways of daphnia were impacted by the nTiO₂ and nTiO₂-algae treatments, including glutathione metabolism, aminoacyl-tRNA biosynthesis, among others. Six and four KEGG metabolic pathways were significantly disturbed in daphnids exposed to nTiO₂ and nTiO₂-algae, respectively, indicating the presence of algae partially alleviated the negative impact of nTiO₂ on metabolism. These findings increase understanding of the impacts of physicochemical properties of nTiO₂ on the food chain from molecular scale to that of the whole organism, and provide new insight into the ecological effect of nanomaterials.

The present study investigated the physiological responses, photosynthetic activity, and microbial community structure of leaf-associated biofilms on the microphyte Vallisneria natans during a harmful algal bloom. Results of the physiological and photosynthetic indices (Fᵥ/Fₘ ratios [maximum quantum yield of photosystem II (PSII)]; malondialdehyde content; total chlorophyll; and activities of superoxide dismutase, catalase and peroxidase) indicated that algal blooms could cause inhibition of photosynthesis, oxidative stress and an antioxidant system stress response in Vallisneria natans leaf-associated biofilms. Multifractal analysis suggested that allelochemicals or algal organic matter released by cyanobacteria could reduce the surface roughness of the leaf. Microbial diversity analysis of the biofilms showed that algal blooms slightly altered the microbial community structure while the richness and evenness of the microbial composition remained stable. This study provided useful information to better understand the adverse effects of algal blooms on submerged macrophytes.

The application of biochar in remediation and recovery of heavy metals and/or organic contaminants in water and soil is increasing. However, the adverse effect of biochar to aquatic organisms has not received enough attention. In this study, we conducted a study on the biotoxicity of biochar pyrolyzed from pine needle under oxygen-limited conditions. The toxicity of biochar was expressed with the following endpoints: cell growth, chlorophyll-a (Chl-a), reactive oxygen species (ROS), superoxide dismutase (SOD) content of Scenedesmus obliquus (S. obliquus) and the luminescence of Photobacterium phosphoreum (P. phosphoreum). Here, the effect of free radicals (FRs) contained in biochar was stressed. Our results show that the toxicity of biochar is significantly correlated with the concentration of FRs in biochar particles. Meanwhile, we found the FRs-containing biochar could induce the production of acellular ROS (such as ·OH) in water, which would also induce the production of interior cellular ROS in aquatic organisms. Our findings provide a new insight into the mechanism of toxicity aroused by biochar applications and aid in understanding its potential ecological risk.

Concerns have been raised regarding the ecotoxicity of ionic liquids (ILs) owing to their wide usage in numerous fields. Three imidazolium chloride ILs with different numbers of methyl substituents, 1-decyl-imidazolium chloride ([C10IM]Cl), 1-decyl-3-methylimidazolium chloride ([C10MIM]Cl), and 1-decyl-2,3-dimethylimidazolium chloride ([C10DMIM]Cl), were examined to assess their effects on growth, photosynthesis pigments content, chlorophyll fluorescence, photosynthetic and respiration rate, and cellular ultrastructure of Scenedesmus obliquus. The results showed that algal growth was significantly inhibited by ILs treatments. The observed IC50,48h doses were 0.10 mg/L [C10IM]Cl, 0.01 mg/L [C10MIM]Cl, and 0.02 mg/L [C10DMIM]Cl. The chlorophyll a, chlorophyll b, and total chlorophyll content declined, and the chlorophyll fluorescence parameters, minimal fluorescence yield (F0), maximal fluorescence yield (Fm), maximum quantum yield of PSII photochemistry (Fv/Fm), effective quantum yield of PSII [Y(II)], non-photochemical quenching (NPQ) and non-photosynthetic losses yield [Y(NO)] were notably affected by ILs in a dose-dependent manner. ILs affected the primary photosynthetic reaction, impaired heat dissipation capability, and diminished photosynthetic efficiency, indicating negative effects on photosystem II. The photosynthetic and respiration rates of algal cells were also reduced due to the ILs treatments. The adverse effects of ILs on plasmolysis and chloroplast deformation were examined using ultrastructural analyses; chloroplast swelling and lamellar structure almost disappeared after the [C10MIM]Cl treatment, and an increased number of starch grains and vacuoles was observed after all ILs treatments. The results indicated that one-methyl-substituted ILs were more toxic than non-methyl-substituted ILs, which were also more toxic than di-methyl-substituted ILs. The toxicity of the examined ILs showed the following order: [C10IM]Cl < [C10DMIM]Cl ≤ [C10MIM]Cl.

Harmful algal blooms have emerged as a worldwide issue. After concentrations of herbicides entering water, herbicides in water may pose ecological effects on them. The present study investigates the toxicity and environmental behavior of the herbicides, napropamide and acetochlor as enantiomers and as racemates on Microcystis aeruginosa which is the main specie known to produce hepatotoxins. S-napropamide/acetochlor are degraded faster than their corresponding isomer R-napropamide/acetochlor, with the latter more prone to accumulate in algal cells. Moreover, all the enantiomers did not undergo measurable racemization in the medium and algal cells. S-napropamide/acetochlor exhibited much higher toxicity than R-napropamide/acetochlor, with the S-enantiomer inducing a much greater production of antioxidant defense enzymes (superoxide dismutase (SOD) and malondialdehyde (MDA)) and microcystins (MC). SOD and MC increased after treatment with the herbicides and these increases were dependent on the exposure time, whereas MDA showed no apparent change. The information provided in this work will be useful for understanding the toxicity mechanism and environmental behaviors of different amide herbicides (napropamide and acetochlor) in aquatic environments at the enantiomeric level. Additionally, analysis of chiral herbicides in aquatic system needs more attention to aide in the environmental assessment of chiral herbicides.

The role of sediment–bound organic phosphorus (Pₒ) as an additional nutrient source is a component of internal P budgets in lake system that is usually neglected. Here we examined the relative importance of sediment Pₒ to internal P load and the role of bioavailable Pₒ in algal growth in Lake Erhai, China. Lake Erhai sediment extractable Pₒ accounted for 11–43% (27% average) of extractable total P, and bioavailable Pₒ accounted for 21–66% (40%) of Pₒ. The massive storage of bioavailable Pₒ represents an important form of available P, essential to internal loads. The bioavailable Pₒ includes mainnly labile monoester P and diester P was identified in the sequential extractions by H₂O, NaHCO₃, NaOH, and HCl. 40% of H₂O−Pₒ, 39% of NaHCO₃−Pₒ, 43% of NaOH−Pₒ, and 56% of HCl−Pₒ can be hydrolyzed to labile monoester and diester P, suggesting that the bioavailability of Pₒ fractions was in decreasing order as follows: HCl−Pₒ > NaOH−Pₒ > H₂O−Pₒ > NaHCO₃−Pₒ. It is implied that traditional sequential fractionation of Pₒ might overestimate the availability of labile Pₒ in sediments. Furthermore, analysis of the environmental processes of bioavailable Pₒ showed that the stabler structure of dissloved organic matter (DOM) alleviated the degradation and release of diester P, abundant alkaline phosphatase due to higher algal biomass promoted the degradation of diester P. The stability of DOM structure and the degradation of diester P might responsible for the spatial differences of labile monoester P. The biogeochemical cycle of bioavailable Pₒ replenishs available P pools in overlying water and further facilitate algal growth during the algal blooms. Therefore, to control the algal blooms in Lake Erhai, an effective action is urgently required to reduce the accumulation of Pₒ in sediments and interrupt the supply cycle of bioavailable Pₒ to algal growth.

The present endocrine disrupting chemicals (EDCs) in wastewater effluents due to incomplete removal during the treatment processes may cause potential ecological and human health risks. This study evaluated the removal and uptake of seven EDCs spiked in two types of wastewater effluent (i.e., ultrafiltration and ozonation) and effluent cultivated with the freshwater green alga Nannochloris sp. In ultrafiltration effluent cultivated with Nannochloris sp. for 7 days, the removal rate of 17β-estradiol (E2), 17α-ethinylestradiol (EE2), and salicylic acid (SAL) was 60%; but Nannochloris sp. did not promote the removal of other EDCs studied. The algal-mediated removal of E2, EE2, and SAL was attributed to photodegradation and biodegradation. Triclosan (TCS) underwent rapid photodegradation regardless of adding algae in the effluent with 63%–100% removal within 7 days. Triclosan was also found associated with algal cells immediately after adding algae, and thus the primary mechanisms involved were photodegradation and bioremoval (i.e., bioadsorption and bioaccumulation). After algal cultivation, TCS still has a bioaccumulation potential to pose high risks within the food web and the endocrine disrupting properties of the residual estrogens in the effluent are not eliminated. Algal cultivation can be exploited to treat wastewater effluents but the removal efficiencies of EDCs highly depend on chemical types.

Dissolved organic carbon (DOC) is not only a critical component of global and regional carbon budgets, but also an important precursor for carcinogenic disinfection byproducts (DBP) generated during drinking water disinfection process. The lack of process based watershed scale model for carbon cycling has been a limiting factor impeding effective watershed management to control DOC fluxes to source waters. Here, we integrated terrestrial and aquatic carbon processes into the widely tested Soil and Water Assessment Tool (SWAT) watershed model to enable watershed-scale DOC modeling (referred to as SWAT-DOC hereafter). The modifications to SWAT mainly fall into two groups: (1) DOC production in soils and its transport to aquatic environment by different hydrologic processes, and (2) riverine transformation of DOC and their interactions with particular organic carbon (POC), inorganic carbon and algae (floating and bottom). We tested the new SWAT-DOC model in the Cannonsville watershed, which is part of the New York City (NYC) water supply system, using long-term DOC load data (from 1998 to 2012) derived from 1399 DOC samplings. The calibration and verification results indicate that SWAT-DOC achieved satisfactory performance for both streamflow and DOC at daily and monthly temporal scales. The parameter sensitivity analysis indicates that DOC loads in the Cannonsville watershed are controlled by the DOC production in soils and its transport in both terrestrial and aquatic environments. Further model uncertainty analysis indicates high uncertainties associated with peak DOC loads, which are attributed to underestimation of high streamflows. Therefore, future efforts to enhance SWAT-DOC to better represent runoff generation processes hold promise to further improve DOC load simulation. Overall, the wide use of SWAT and the satisfactory performance of SWAT-DOC make it a useful tool for DOC modeling and mitigation at the watershed scale.

Swampy/septic odors are one of the most important odor types in drinking water. However, few studies have specifically focused on it compared to the extensive reported musty/earthy odor problems, even though the former is much more offensive. In this study, an investigation covering the odor characteristics, algal distribution and possible odorants contributing to swampy/septic odor, including dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), diisopropyl sulfide (DIPS), dipropyl sulfide (DPS), dibutyl sulfide (DBS), 2-methylisoborneol (2-MIB) and geosmin (GSM), was performed in source and finished water of 56 drinking water treatment plants (DWTPs) in 31 cities across China. While the musty/earthy and swampy/septic odors were dominant odor descriptors, the river source water exhibited a higher proportion of swampy/septic odor (38.5%) compared to much higher detection rate of musty/earthy odor (50.0%) in the lake/reservoir source water. The occurrence of swampy/septic odor, which was much easier to remove by conventional drinking water treatment processes compared to musty/earthy odors, was decreased by 62.9% and 46.3% in river and lake/reservoir source water respectively. Statistical analysis showed that thioethers might be responsible for the swampy/septic odor in source water (R2 = 0.75, p < 0.05). Specifically, two thioethers, DMDS and DMTS were detected, and other thioethers were not found in all water samples. DMDS was predominant with a maximum odor activity value (OAV) of 2.0 in source water and 1.3 in finished water. The distribution of the thioethers exhibited a marked regional characteristics with higher concentrations being detected in the east and south parts of China. The high concentrations of thioethers in lake/reservoir source water samples could be partly interpreted as the bloom of the cyanobacteria. This study provides basic information for swampy/septic odor occurrence in drinking water and will be helpful for further water quality management in water industry in China.

In the present investigation seaweeds of macroalgae like Kappaphycus alvarezii, Gracilaria salicornia and Gracilaria edulis used as novel biosorbent in native (KA, GS, GE) and ethanol modified (EKA, EGS, EGE) for Rhodamine B (RB) removal from aqueous solution in batch process. Effect of various biosorption parameters such as pH, initial concentration of RB, biosorbent dosage and contact time were studied. The maximum biosorption capacity determined as 9.84 (KA), 11.03 (GS), 8.96 (GE), 112.35 (EKA), 105.26 (EGS) and 97.08 mg/g (EGE), respectively towards the removal of RB from aqueous solutions. Better removal of RB was observed using EKA, EGS, and EGE biosorbents at 2.0 pH. The characterizations of the biosorbents were performed using Scanning Electron microscope and Fourier Transform Infrared Spectroscopy. Biosorption equilibrium data evaluated using Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Jovanovic isotherm model. The Langmuir isotherm model best suited the equilibrium data for all the biosorbents studied. The rate of RB removal subjected to kinetic analysis using pseudo-first-order, pseudo-second-order, intra-particle diffusion and Elovich models. Pseudo-second-order kinetic model better described the experimental data of the RB biosorption. Desorption studies performed using 0.1 M sodium hydroxide as eluting agents for regeneration and recycle analysis. The recyclability of the six biosorbents showed consistent biosorption capacity towards RB removal up to the entire three cycles. The studied biosorbents sourced from large volume and easily available, further biosorption performance indicated that the KA, GS, GE, EKA, EGS and EGE could be used as efficient, alternative and eco-friendly biosorbents for the removal of harmful dyes in the environment.