A laboratory study of the increasing competitiveness of Karenia mikimotoi under rising CO2 scenario.

Ocean acidification (OA) driven by elevated carbon dioxide (CO2) levels is expected to disturb marine ecological processes, including the formation and control of harmful algal blooms (HABs). In this study, the effects of rising CO2 on the allelopathic effects of macroalgae Ulva pertusa to a toxic dinoflagellate Karenia mikimotoi were investigated. It was found that high level of CO2 (1000 ppmv) promoted the competitive growth of K. mikimotoi compared to the group of present ambient CO2 level (420ppmv), with the number of algal cell increased from 32.2 × 104 cells/mL to 36.75 × 104 cells/mL after 96 h mono-culture. Additionally, rising CO2 level weakened allelopathic effects of U. pertusa on K. mikimotoi, as demonstrated by the decreased inhibition rate (50.6 % under the original condition VS 34.3 % under the acidified condition after 96 h co-culture) and the decreased reactive oxygen species (ROS) level, malondialdehyde (MDA) content, antioxidant enzymes activity (superoxide dismutase (SOD), peroxidase (POD), glutathione peroxidase (GPX), glutathione reductase (GR) and catalase (CAT) and non-enzymatic antioxidants (glutathione (GSH) and ascorbic acid (ascorbate, vitamin C). Indicators for cell apoptosis of K. mikimotoi including decreased caspase-3 and -9 protease activity were observed when the co-cultured systems were under rising CO2 exposure. Furthermore, high CO2 level disturbed fatty acid synthesis in U. pertusa and significantly decreased the contents of fatty acids with allelopathy, resulting in the allelopathy weakening of U. pertusa. Collectively, rising CO2 level promoted the growth of K. mikimotoi and weakened allelopathic effects of U. pertusa on K. mikimotoi, indicating the increased difficulties in controlling K. mikimotoi using macroalgae in the future.

Improving bioelectrochemical performance by sulfur-doped titanium dioxide cooperated with Zirconium based metal-organic framework (S-TiO2@MOF-808) as cathode in microbial fuel cells.

The sulfur-doped titanium dioxide (S-TiO2) cooperated with Zirconium based on a kind of metal-organic framework (MOF-808) was successfully prepared as cathode catalyst (S-TiO2@MOF-808) of microbial fuel cell (MFC) by two-step hydrothermal reaction. The particle size was approximately 5 µm, and the spherical S-TiO2 particle was attached to the surface of MOF-808 as irregular block solid. Zr-O, C-O and O-H bond were indicated to exist in S-TiO2@MOF-808. When n (Zr4+): n(Ti4+) was 1: 5, S-TiO2@MOF-808 showed better oxygen reduction reaction (ORR). The introduction of S-TiO2 restrained the framework collapse of MOF-808, S-TiO2@MOF-808 showed much higher catalytic stability in reaction. The recombination of sulfur and TiO2 reduced the charge transfer resistance, accelerated the electron transfer rate, and improved ORR greatly. The maximum power density of S-TiO2@MOF-808-MFC was 84.05 mW/m2, about 2.17 times of S-TiO2-MFC (38.64 mW/m2). The maximum voltage of S-TiO2@MOF-808-MFC was 205 mV, and the stability was maintained for 6 d.

Research status and prospects of organic photocatalysts in algal inhibition and sterilization: a review.

An increasing amount of sewage has been discharged into water bodies in the progression of industrialization and urbanization, causing serious water pollution. Meanwhile, the increase of nutrients in the water induces water eutrophication and rapid growth of algae. Photocatalysis is a common technique for algal inhibition and sterilization. To improve the utilization of visible light and the conversion efficiency of solar energy, more organic photocatalytic materials have been gradually developed. In addition to ultraviolet light, partial infrared light and visible light could also be used by organic photocatalysts compared with inorganic photocatalysts. Simultaneously, organic photocatalysts also exhibit favorable stability. Most organic photocatalysts can maintain a high degradation rate for algae and bacteria after several cycles. There are various organic semiconductors, mainly including small organic molecules, such as perylene diimide (PDI), porphyrin (TCPP), and new carbon materials (fullerene (C60), graphene (GO), and carbon nanotubes (CNT)), and large organic polymers, such as graphite phase carbon nitride (g-C3N4), polypyrrole (PPy), polythiophene (PTH), polyaniline (PANI), and polyimide (PI). In this review, the classification and synthesis methods of organic photocatalytic materials were elucidated. It was demonstrated that the full visible spectral response (400-750 nm) could be stimulated by modifying organic photocatalysts. Moreover, some problems were summarized based on the research status related to algae and bacteria, and corresponding suggestions were also provided for the development of organic photocatalytic materials.

"Needle" hidden in silk floss: Inactivation effect and mechanism of melamine sponge loaded bismuth oxide composite copper-metal organic framework (MS/Bi2O3@Cu-MOF) as floating photocatalyst on Microcystis aeruginosa.

Photocatalytic technology showed significant potential for addressing the issue of cyanobacterial blooms resulting from eutrophication in bodies of water. However, the traditional powder materials were easy to agglomerate and settle, which led to the decrease of photocatalytic activity. The emergence of floating photocatalyst was important for the practical application of controlling harmful algal blooms. This study was based on the efficient powder photocatalyst bismuth oxide composite copper-metal organic framework (Bi2O3 @Cu-MOF), which was successfully loaded onto melamine sponge (MS) by sodium alginate immobilization to prepare a floating photocatalyst MS/Bi2O3 @Cu-MOF for the inactivation of Microcystis aeruginosa (M. aeruginosa) under visible light. When the capacity was 0.4 g (CA0.4), MS/Bi2O3 @Cu-MOF showed good photocatalytic activity, and the inactivation rate of M. aeruginosa reached 74.462% after 120 h. MS/Bi2O3 @Cu-MOF-CA0.4 showed a large specific surface area of 30.490 m2/g and an average pore size of 22.862 nm, belonging to mesoporous materials. After 120 h of treatment, the content of soluble protein in the MS/Bi2O3 @Cu-MOF-CA0.4 treatment group decreased to 0.365 mg/L, the content of chlorophyll a (chla) was 0.023 mg/L, the content of malondialdehyde (MDA) increased to 3.168 nmol/mgprot, and the contents of various antioxidant enzymes experienced drastic changes, first increasing and then decreasing. The photocatalytic process generated·OH and·O2-, which played key role in inactivating the algae cells. Additionally, the release of Cu2+ and adsorption of the material also contributed to the process.

Hyperspectral estimation of chlorophyll content in jujube leaves: integration of derivative processing techniques and dimensionality reduction algorithms.

The leaf chlorophyll content (LCC) of vegetation is closely related to photosynthetic efficiency and biological activity. Jujube (Ziziphus jujuba Mill.) is a traditional economic forest tree species. Non-destructive monitoring of LCC of jujube is of great significance for guiding agroforestry production and promoting ecological environment protection in arid and semi-arid lands. Hyperspectral data is an important data source for LCC detection. However, hyperspectral data consists of a multitude of bands and contains extensive information. As a result, certain bands may exhibit high correlation, leading to redundant spectral information. This redundancy can distort LCC prediction results and reduce accuracy. Therefore, it is crucial to select appropriate preprocessing methods and employ effective data mining techniques when analyzing hyperspectral data. This study aims to evaluate the performance of hyperspectral data for estimating LCC of jujube trees by integrating different derivative processing techniques with different dimensionality reduction algorithms. Hyperspectral reflectance data were obtained through simulations using an invertible forest reflectance model (INFORM) and measurements from jujube tree canopies. The least absolute shrinkage and selection operator (LASSO) and elastic net (EN) were employed to identify the important bands in the original spectra (OS), first derivative spectra (FD), and second derivative spectra (SD). Support vector regression (SVR) was used to establish the estimation model. The results show that compared with full-spectrum modeling, LASSO and EN algorithms are effective methods for preventing overfitting in LCC machine learning estimation models for different spectral derivatives. The LASSO/EN-based estimation models constructed using FD and SD exhibited superior R2 compared to the OS. The important band of SD can best reveal the relevant information of jujube LCC, and SD-EN-SVR is the most ideal model in both the simulated dataset (R2 = 0.99, RMSE=0.61) and measured dataset (R2 = 0.89, RMSE=0.91). Our results provided a reference for rapid and non-destructive estimation of the LCC of agroforestry vegetation using canopy hyperspectral data.

The selection of floating photocatalyst carrier and algae inhibition effect of Karenia mikimotoi based on SNP-TiO2@Cu-MOF under visible light.

Photocatalytic technology for inactivating harmful algae has shown great research potential, in previous work, a kind of non-noble metal modified TiO2 loading onto copper metal organic framework (SNP-TiO2@Cu-MOF) was proved to show high removal efficiency against Karenia mikimotoi (K. mikimotoi). However, the recovery problem of powdered photocatalysts and its potential ecological hazards were still existed. In order to solve this, this study selected four macro-floating carriers and loaded photocatalyst on their surface. The floating photocatalyst with luffa sponge and expanded perlite as carriers were prepared by hydrothermal synthesis, and the floating photocatalyst with melamine sponge and polyurethane sponge as carriers were prepared by sodium alginate fixation method. The photocatalyst was firmly supported on the carriers, and the octahedral structure of SNP-TiO2@Cu-MOF photocatalyst could be well retained by hydrothermal synthesis. The advantages of sodium alginate fixation method were simple preparation process and low cost. The specific surface area of melamine foam photocatalyst (MF-P) was the highest, 28.47 m2/g, and the algae inactivation rate was also the best, which was 98.68% in 6 h. The MF-P group showed a decrease of 81.8% in soluble protein content and 81.4% in chlorophyll-a content of K. mikimotoi after 1 h of photocatalysis, respectively. The four photocatalysts showed good recyclability, and especially in MF-P group. The inactivation efficiency was still as high as 94.12% after four experiments. The floating photocatalyst would lay the foundation for further application of photocatalytic materials for algae removal.

Toxicological evaluation of TBBPA by common carp (Cyprinus carpio) about the in vivo/vitro disturbance of the AHR pathway.

Tetrabromobisphenol A (TBBPA) is a widely used plastic additive with high bioaccumulation potential and toxicity on both humans and wildlife. Currently, research on its ecotoxicity and the underlying mechanism is limited. Using common carp (Cyprinus carpio), we evaluated the toxicity of TBBPA, especially focusing on its alteration of a key metabolism-related pathway aryl hydrocarbon receptor (AHR), using in vivo/vitro assays and in silico simulation. The 96 h LC50 of TBBPA of common carp was 4.2 mg/L and belonged to the acute toxic level II. The bioaccumulation potential of TBBPA follows the role of liver > gill > brain and varies between 3- and 14-day exposure. On the AHR pathway respect, as expected, the metabolism-related cyp1a1 and cyp1b1 were upregulated in the liver and brain. Ahr2, the receptor, was also upregulated in the brain under TBBPA exposure. The alteration of gene expression was tissue-specific while the difference between 3- or 14-day exposure was minor. AHR inhibition assay indicated the 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD)-induced AHR transactivation can be inhibited by TBBPA suggesting it is not a potent agonist but a competitive antagonist. In silico analysis indicated TBBPA can be successfully docked into the binding cavity with similar poses but still have AHR-form-specific interactions. Molecular dynamics simulation proved TBBPA can be more flexible than the coplanar ligand TCDD, especially in ccaAHR1b with greater root-mean-square deviation (RMSD), of which TCDD-induced transactivation seemed not to be blocked by TBBPA. This research increased the understanding of TBBPA toxicity and alteration of the AHR pathway, and pointed out the need to perform additional toxicology evaluation of emerging contaminants, especially on non-model species.

Adsorption of hexavalent chromium, Rhodamine B and Congo red simultaneously in aquatic by zeolitic imidazolate framework coupling carbon nanotubes.

Zeolitic imidazolate framework/carbon nanotube (ZIF-67/CNTs) was prepared by precipitation method. ZIF-67/CNTs maintained the characteristics of large specific surface area and high porosity of ZIFs, showing stable cubic structure. The adsorption capacities of ZIF-67/CNTs for Cong red (CR), Rhodamine B (RhB) and Cr(VI) were 36.82 mg/g, 1421.29 mg/g and 716.67 mg/g under the conditions of 2:1, 3:1 and 1:3 masses of ZIF-67 and CNTs, respectively. The optimum adsorption temperature of CR, RhB and Cr(VI) were 30 °C, and the removal rates at the adsorption equilibrium were 81.22%, 72.87% and 48.35%. The adsorption kinetic model of the three adsorbents on ZIF-67/CNTs was consistent with the quasi-second order reaction model, and the adsorption isotherms were more consistent with adsorption law of Langmuir. The adsorption mechanism for Cr(VI) was mainly electrostatic interaction, and the adsorption mechanism for azo dyes was the combination of physical and chemical adsorption. This study would provide theoretical basis for further developing metal organic framework (MOF) materials for environmental applications.

Trace N-doped manganese dioxide cooperated with Ping-pong chrysanthemum-like NiAl-layered double hydroxide on cathode for improving bioelectrochemical performance of microbial fuel cell.

Trace N-doped manganese dioxide (MnO2) nanoparticles were attached to NiAl-layered double hydroxide (LDH) nano sheets by a simple two-step hydrothermal reaction, and N-MnO2@NiAl-LDH was successfully prepared as cathode catalyst of microbial fuel cell (MFC). N-MnO2@NiAl-LDH was Ping-pong chrysanthemum-like structure formed by overlapping lamellar structures, with spherical MnO2 particles attached on. The unique Ping-pong chrysanthemum-like structure and pore size distribution provided large number of electrochemical active sites. The recombination of trace N and MnO2 reduced the charge transfer resistance, accelerated the electron transfer rate, and N-MnO2@NiAl-LDH showed high oxygen reduction reaction (ORR) capability. The maximum output power density of N-MnO2@NiAl-LDH-MFC was 698 mW/m2, about 4.59 times of NiAl-LDH (152.1 mW/m2). The maximum voltage was about 320 mV, and the stability was good for about 7 d. This would provide technical reference for the utilization of cathode catalyst for fuel cells.

Functional characterization of common carp (Cyprinus carpio) AHRs: Subform-specific sensitivity to dioxin and interspecies differences.

Dioxins are widely known to bioaccumulate in the body and produce a wide spectrum of toxic effects on both humans and wildlife. In addition, some novel sorts of compounds that were similar in structure and effect were gradually identified and termed dioxin-like compounds (DLCs). The toxicity of dioxins as well as DLCs is predominantly mediated by the dioxin receptor (aryl hydrocarbon receptor, AHR) in animals, which is usually differentially expressed and functionally distinct (especially the sensitivity to dioxins) among species, possibly resulting in species-specific variations in the toxicity of dioxins. Therefore, detailed functional exploration of the AHRs of a given species, such as the common carp (which is a vital wild and commercial species with a broad geological distribution) in the current study, will enable a comprehensive ecotoxicity evaluation. Through genome survey and phylogenetic analysis, we identified three AHRs (AHR1a, AHR1b, and AHR2) and two ARNTs (ARNT1 and ARNT2). AHR2 was observed to have greater expression abundance in the gill and brain, and may serve as the predominant subform. Those AHRs and ARNTs are functional, and the AHRs can be efficiently transactivated by the classical dioxin congener 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). We individually determined the EC50 values of AHR1a (0.41 ± 0.24 nM), AHR1b (12.80 ± 3.28 nM), and AHR2 (0.64 ± 0.49 nM), and found that: 1) The AHR sensitivities of common carp and zebrafish (phylogenetically close species) are relatively similar. AHR1a and the predominant form AHR2 have greater sensitivity to TCDD. 2) ARNT1 and ARNT2 do not produce different sensitivities, but with distinct induction fold, of a given AHR transactivation when cooperating as the partner; 3) Distinct AHR subforms of the same or distinct species can have even one or two orders of magnitude differences in sensitivity. In summary, the current study will add to the knowledge of AHR biology and help improve ecotoxicology research on dioxins and DLCs.

Regional distribution of the plastic additive tris(butoxyethyl) phosphate in Nanyang Lake estuary, China, and toxic effects on Cyprinus carpio.

There is increasing concern regarding the toxicological effects of plastic additives on humans and aquatic organisms. This study investigated effects of the plastic additive tris(butoxyethyl) phosphate (TBEP) on Cyprinus carpio by measuring concentration distribution of TBEP in the Nanyang Lake estuary, as well as toxic effects of varying doses of TBEP exposure on carp liver. This also included measuring responses of superoxide dismutase (SOD), malondialdehyde (MDA), tumor necrosis factor-α (TNF-α), interleukin-1ß (IL-1ß), and cysteinyl aspartate-specific protease (caspase). Concentrations of TBEP in the polluted water environment (water company inlets, urban sewage pipes, etc.) in the survey area were as high as 76.17-3875.29 µg/L, and 3.12 µg/L in the river flowing through the urban area, and 1.18 µg/L in the estuary of the lake. In the subacute toxicity test, SOD activity in liver tissue with an increase in TBEP concentration was reduced significantly, while the MDA content continued to increase with an increase in TBEP concentration. Inflammatory response factors (TNF-α and IL-1ß) and apoptotic proteins (caspase-3 and caspase-9) gradually increased with increasing concentrations of TBEP. Additionally, reduced organelles, increased lipid droplets, swelling of mitochondria, and disorder of mitochondrial cristae structure were observed in liver cells of TBEP-treated carp. Generally, TBEP exposure induced severe oxidative stress in carp liver tissue, resulting in release of inflammatory factors and inflammatory response, mitochondrial structure changes, and the expression of apoptotic proteins. These findings benefit our understanding about the toxicological effects of TBEP in aquatic pollution.

Improved bioelectrochemical performance of MnO2 nanorods modified cathode in microbial fuel cell.

The property of cathode in the microbial fuel cell (MFC) was one of the key factors limiting its output performance. MnO2 nanorods were prepared by a simple hydrothermal method as cathode catalysts for MFCs. There were a number of typical characteristic crystal planes of MnO2 nanorods like (110), (310), (121), and (501). Additionally, there were great many hydroxyl groups on the surface of nanorod-like MnO2, which provided a rich set of active adsorption sites. The maximum power density (Pmax) of MnO2-MFC was 180 mW/m2, which was 1.51 times that of hydrothermally synthesized MnO2 (119.07 mW/m2), 4.28 times that of naturally synthesized MnO2 (42.05 mW/m2), and 5.61 times that of the bare cathode (32.11 mW/m2). The maximum voltage was 234 mV and the maximum stabilization time was 4 days. The characteristics of MnO2, including rod-like structure, high specific surface area, and high conductivity, were conducive to providing more active sites for oxygen reduction reaction (ORR). Therefore, the air cathode modified by MnO2 nanorods was a kind of fuel cell electrode with great application potential.

Highly efficient and recyclable Z-scheme heterojunction of Ag3PO4/g-C3N4 floating foam for photocatalytic inactivation of harmful algae under visible light.

Harmful algal blooms (HABs) have frequently occurred worldwide, causing marine ecosystems and human health risks. As an advanced and green oxidation technology, photocatalysis has potential to remove red tide algae using solar energy. Herein, in this work, Z-scheme photocatalysts of Ag3PO4/g-C3N4 (APCN) floating foam with different mass ratios were fabricated for the algae inactivation. Under visible light irradiation, the 0.10APCN (0.10 mM AgNO3) composite photocatalyst could cause 91.8% of the loss in Karenia mikimotoi (K. mikimotoi) cell viability following 24 h and the removal rate of algae could reach to 86% after five successive cycles. The underlying mechanism of photocatalytic inactivation of harmful algae is proposed in this system. The photosynthetic efficiency of harmful algae is inhibited with the decrease of photosynthetic pigments, which are inactivated by the high levels of reactive oxygen species (ROS) (superoxide radical •O2- and hydroxyl radical •OH) produced in Z-scheme photocatalytic system of the Ag3PO4/g-C3N4 heterojunction under visible light. Meanwhile, the activities of antioxidant enzymes (i.e. POD, APX and SOD) are up-regulating with the overproduction of ROS going into the algae, causing the cytotoxicity and apoptosis of algae. This work not only reveals the mechanisms of photocatalytic inactivation of harmful algae, but also guides the design the construction of high active composite photocatalysts, and thus provides theoretical and practical significance for highly efficient and recyclable prospect of controlling of harmful algae.

Metabolites and metabolic pathways associated with allelochemical effects of linoleic acid on Karenia mikimotoi.

Linoleic acid (LA) shows great potential in inhibiting the growth of multiple red tide microalgae by disturbing algal physio-biochemical processes. However, our knowledge on the mechanisms of algal mortality at metabolic level remains limited. Herein, the response of K. mikimotoi to LA was evaluated using metabolomics, stable isotope techniques (SIT), and physiological indicators. Results showed that 100 µg/L LA promoted the growth of K. mikimotoi, which was significantly inhibited by 500 µg/L LA, along with a significant reduction of photosynthetic pigments and a significant increase of reactive oxygen species (ROS). SIT showed that LA entered algal cells, and 56 isotopologues involved in ferroptosis, carotenoid biosynthesis, and porphyrin metabolism were identified. Non-targeted metabolomics identified 90 and 111 differential metabolites (DEMs) belonging to 11 metabolic pathways under the 500 µg/L and 100 µg/L LA exposure, respectively. Among them, 34 DEMs were detected by SIT. Metabolic pathway analysis showed that 500 µg/L LA significantly promoted ferroptosis, and significantly inhibited carotenoid biosynthesis, porphyrin metabolism, sphingolipid metabolism, and lipopolysaccharide biosynthesis, presenting changes opposite to those observed in 100 µg/L LA-treated K. mikimotoi. Overall, this study revealed the metabolic response of K. mikimotoi to LA, enriching our understanding on the allelochemical mechanism of LA on K. mikimotoi.

A pathway for promoting bioelectrochemical performance of microbial fuel cell by synthesizing graphite carbon nitride doped on single atom catalyst copper as cathode catalyst.

In this study, a simple distributed feeding method was used to dope graphite phase carbon nitride (g-C3N4) on single atom catalyst (SAC) copper (Cu) to form composite material (Cu-SA/CN). Cu-SA/CN was formed by mutual doping of polyhedral block Cu and irregular g-C3N4. There were obvious crystal face peaks at 28.4, 43.3, 47.3 and 56.2°. Large solid Cu and small irregular g-C3N4 were successfully combined and C, Cu, N and O elements were uniformly distributed on the surface of Cu-SA/CN. The valence bond of N-CN, C-NC, CC and OH was found. When the Cu content was 0.03 mol, Cu-SA/CN3 showed excellent redox activity. The maximum power density of Cu-SA/CN3-MFC was 456.976 mW/m2, the maximum voltage was 599 mV, which could be stable for 7 d. Cu-SA/CN3 was proved to provide more electrically active sites, strong catalytic oxygen reduction ability and conductivity.

Effects comparison between the secondary nanoplastics released from biodegradable and conventional plastics on the transfer of antibiotic resistance genes between bacteria.

Antibiotic resistance genes (ARGs) have caused widespread concern because of their potential harm to environmental safety and human health. As substitutes for conventional plastics, the toxic effects of short-term degradation products of biodegradable plastics (polylactic acid (PLA) and polyhydroxyalkanoates (PHA)) on bacteria and their impact on ARGs transfer were the focus of this study. After 60 days of degradation, more secondary nanoplastics were released from the biodegradable plastics PLA and PHA than that from the conventional plastics polystyrene (PS). All kinds of nanoplastics, no matter released from biodegradable plastics or conventional plastics, had no significant toxicity to bacteria. Nanoplastic particles from biodegradable plastics could significantly increase the transfer efficiency of ARGs. Although the amount of secondary nanoplastics produced by PHA microplastics was much higher than that of PLA, the transfer frequency after exposure to PLA was much higher, which may be due to the agglomeration of PHA nanoplastics caused by plastic instability in solution. After exposure to the 60 d PLA nanoplastics, the transfer frequency was the highest, which was approximately 28 times higher than that of control. The biodegradable nanoplastics significantly enhanced the expression of the outer membrane pore protein genes ompA and ompC, which could increase cell membrane permeability. The expression levels of trfAp and trbBp were increased by repressed major global regulatory genes korA, korB, and trbA, which eventually led to an increase in conjugative transfer frequency. This study provides important insights into the evaluation of the environmental and health risks caused by secondary nanoplastics released from biodegradable plastics.

Roles of extracellular polymeric substances on Microcystis aeruginosa exposed to different sizes of polystyrene microplastics.

Extracellular polymeric substances (EPS) are important shields for microalgae when confronting with external stresses. However, the underlying roles of EPS in the interactions between microplastics (MPs) and microalgae remain poorly understood. In this study, three sizes of polystyrene (PS) MPs (20 nm, 100 nm, and 1 µm) were chosen for evaluating the compositions of EPS, secreted by Microcystis aeruginosa during exposure. The results indicated that the EPS compositions were different when M. aeruginosa was exposed to PS MPs of different sizes. The presence of EPS is helpful for alleviating the adverse effects of PS MPs on M. aeruginosa cell growth, photosynthesis, and oxidative stress. With the exception of the shading effect, insufficient EPS cause direct adsorption of unstable 1 µm PS MPs to the algal surface, which could destroy the cell wall. In contrast, aromatic proteins and fulvic acids are representative EPS components stimulated by 100 nm PS MPs, contributing to the self-aggregation and encapsulation of algal cells and availability of nutrients for algal growth, respectively. High amounts of polysaccharides were secreted by M. aeruginosa along with humic acids during exposure to 20 nm PS MPs, both of which are crucial in the homo-aggregation of 20 nm PS MPs toward minimize its adverse effects on M. aeruginosa. Together, these findings revealed the differences in EPS under the stimulation of PS MPs of different sizes and clarified the roles of different EPS components in resisting the adverse effects of PS MPs on M. aeruginosa.

A critical review of research progress for metal alloy materials in hydrogen evolution and oxygen evolution reaction.

Hydrogen produced by electrolyzing water has attracted extensive attention as an effective way to generate and store new energy by using renewable energy. Electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were the core reactions in the process of hydrogen production by water electrolysis, however, due to the low efficiency of the electrolytic device caused by its slow kinetic reaction and the dependence on noble metal catalysts (platinum and iridium/ruthenium (oxide)), which limited its wide application. The preparation of high-efficiency catalysts with high catalytic activity, stability, low cost and scalability played a vital role in promoting the development of hydrogen production technology from electrolytic water and has become a current research hotspot. Metal alloy catalysts have been widely studied as high-efficiency electrocatalysts. This study introduced and analyzed the mechanism and application of metal alloy catalyst in hydrogen and oxygen evolution reaction, summarized and discussed the progress in the design, preparation and application of metal alloy electrocatalysts. Finally, the strategy and prospect of new high-efficiency electrocatalysts were proposed.

Acidification of seawater attenuates the allelopathic effects of Ulva pertusa on Karenia mikimotoi.

Acidification of seawater resulting from absorption of excessive carbon dioxide from the atmosphere is posing a serious threat to marine ecosystem. In this study, we hypothesized that acidified seawater attenuates allelopathic effects of macroalgae on red tide algae because the increase of dissolved carbon dioxide benefits algal growth, and investigated the allelopathic effects of Ulva pertusa on Karenia mikimotoi in response to seawater acidification by determining cell density, photosynthetic pigment content, chlorophyll fluorescence parameters, and chloroplast structure of K. mikimotoi under U. pertusa stress in original (pH=8.2) and acidified (pH=7.8) seawater. U. pertusa inhibited the growth of K. mikimotoi in the original and acidizing seawater, and the inhibition rate was positively correlated with treatment time and concentration of U. pertusa. However, acidizing condition significantly weakened the inhibition degree of U. pertusa on K. mikimotoi (P < 0.05), with the inhibition rates decreased from 51.85 to 43.16% at 10 gFW/L U. pertusa for 96 h. U. pertusa reduced contents of chlorophyll a, chlorophyll c, and carotenoid, maximum photochemical quantum yield (Fv/Fm), actual quantum yield, maximum relative electron transfer efficiency (rETRmax) of PSII, real-time fluorescence value (F), and maximum fluorescence value (Fm') of PSII of K. mikimotoi under original and acidified conditions. And, the inhibition degree of U. pertusa under acidizing condition was significantly lower than that of original seawater group. Furthermore, the damage degree of chloroplast structure of K. mikimotoi under U. pertusa stress was more serious under original seawater condition. These results indicate that acidification of seawater attenuates the allelopathic effects of U. pertusa on K. mikimotoi.

Photocatalytic degradation effect and mechanism of Karenia mikimotoi by non-noble metal modified TiO2 loading onto copper metal organic framework (SNP-TiO2@Cu-MOF) under visible light.

In this study, the SNP-TiO2@Cu-MOF composite was prepared successfully by loading non-noble metal modified TiO2 (SNP-TiO2) on the surface of copper metal organic skeleton (Cu-MOF), and compared the inactivation efficiency of different photocatalysts to Karenia mikimotoi (K. mikimotoi) under visible light. The obtained photocatalyst had the characteristic crystal faces of Cu-MOF and SNP- TiO2, and contained functional groups such as Cu-O, -COOH, N-O, P-O, etc., which indicated the structural stability of the photocatalyst. The band gap of SNP-TiO2@Cu-MOF composite was 2.82 eV, and it had great light absorption ability in visible light region. It was proved to be a mesoporous adsorption material, which had a huge specific surface area (245 m2/g). Compared with other photocatalysts, SNP-TiO2@Cu-MOF composite showed the strongest photocatalytic activity. When the concentration of composite material was set to 100 mg/L and the exposure time was 6 h, the visible light photocatalytic inactivation efficiency of K. mikimotoi was 93.75 %. By measuring various metabolic indexes of K. mikimotoi under the action of different photocatalysts for 1 h, it was confirmed that cell inactivation was due to the increased membrane permeability and degradation of photosynthetic pigments and main life proteins. This research showed that SNP-TiO2@Cu-MOF composite material was full of great potential and application prospect in controlling the outbreak of eutrophication.