Dynamic orbital hybridization triggered spin-disorder renormalization via super-exchange interaction for oxygen evolution reaction.

The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.

Mechanisms and Strategies of Advanced Oxidation Processes for Membrane Fouling Control in MBRs: Membrane-Foulant Removal versus Mixed-Liquor Improvement.

Membrane bioreactors (MBRs) are well-established and widely utilized technologies with substantial large-scale plants around the world for municipal and industrial wastewater treatment. Despite their widespread adoption, membrane fouling presents a significant impediment to the broader application of MBRs, necessitating ongoing research and development of effective antifouling strategies. As highly promising, efficient, and environmentally friendly chemical methods for water and wastewater treatment, advanced oxidation processes (AOPs) have demonstrated exceptional competence in the degradation of pollutants and inactivation of bacteria in aqueous environments, exhibiting considerable potential in controlling membrane fouling in MBRs through direct membrane foulant removal (MFR) and indirect mixed-liquor improvement (MLI). Recent proliferation of research on AOPs-based antifouling technologies has catalyzed revolutionary advancements in traditional antifouling methods in MBRs, shedding new light on antifouling mechanisms. To keep pace with the rapid evolution of MBRs, there is an urgent need for a comprehensive summary and discussion of the antifouling advances of AOPs in MBRs, particularly with a focus on understanding the realizing pathways of MFR and MLI. In this critical review, we emphasize the superiority and feasibility of implementing AOPs-based antifouling technologies in MBRs. Moreover, we systematically overview antifouling mechanisms and strategies, such as membrane modification and cleaning for MFR, as well as pretreatment and in-situ treatment for MLI, based on specific AOPs including electrochemical oxidation, photocatalysis, Fenton, and ozonation. Furthermore, we provide recommendations for selecting antifouling strategies (MFR or MLI) in MBRs, along with proposed regulatory measures for specific AOPs-based technologies according to the operational conditions and energy consumption of MBRs. Finally, we highlight future research prospects rooted in the existing application challenges of AOPs in MBRs, including low antifouling efficiency, elevated additional costs, production of metal sludge, and potential damage to polymeric membranes. The fundamental insights presented in this review aim to elevate research interest and ignite innovative thinking regarding the design, improvement, and deployment of AOPs-based antifouling approaches in MBRs, thereby advancing the extensive utilization of membrane-separation technology in the field of wastewater treatment.

Comparative Analysis of Clinical Outcomes: Posterior Cervical Endoscopic Discectomy versus Fenestration Laminectomy Discectomy for Cervical Disc Herniation.

Objective: It aimed to investigate the difference in clinical efficacy between posterior cervical endoscopic discectomy (PCED) and Fenestration laminectomy discectomy (FLD) in cervical disc herniation (CDH). Methods: This retrospective study analyzed 100 CDH patients undergoing nucleotomy and assigned them into the FLD and PCED groups, 50 cases for each group. The differences in operation time, intraoperative blood loss, skin incision, off-bed time, and hospital stay were evaluated. Numeric rating scales (NRS), Oswestry disability Index (ODI), Japanese Orthopaedic Association (JOA), excellent and good clinical efficacy, quality of life (QoL) SF-36 score, and complication rate were compared. Results: The results showed that compared with the FLD group, the PCED group had increased operation time, decreased intraoperative blood loss, skin incision length, off-bed time, and hospital stay (P < .01). Compared with the FLD group, the PCED group had decreased NRS and ODI scores and increased JOA scores at 1 d, 3 d, 1 month, 3 months, 6 months, 12 months, and 24 months after operation (P < .05). Compared with the FLD group, the excellent and good rate of the PCED group increased significantly after 6 months, 1 year, and 2 years (52.0% vs 64.0%, 58.0% vs. 80.0%, 68.0% vs 90.0%, P < .05). Relative to the FLD group, the physical function, emotional function, vitality, social function, and mental health score of the PCED group increased obviously at 2 years after operation (P < .01). The postoperative complication rate was 0% in both FLD and PCED groups. PCED has good long-term clinical efficacy in the treatment of CDH, with excellent recovery and high safety. Conclusion: PCED showed favorable long-term clinical efficacy in the treatment of CDH, with excellent recovery and high safety. Compared to FLD, PCED resulted in reduced intraoperative blood loss, shorter incision length, and faster recovery. It also led to improved pain scores, functional outcomes, and quality of life measures. The absence of postoperative complications further supports the use of PCED as an effective treatment option for CDH.

Agricultural practices and ditch size drive microbial community assembly and mediate N- and P-transformation in multistage drainage networks of paddy fields: Insights from a large-scale irrigation district in eastern China.

Agricultural drainage ditches (ADDs) are ubiquitous and regarded as active zones for biogeochemical reactions and microbe-mediated pollutant removal. However, little is known about the microbial distribution and community assembly in ADDs. Here, a typical large-scale irrigation district, including five orders of farmland drainage systems (namely field, sublateral, head, branch, and trunk ditches that could efficiently remove excess water from paddy fields to downstream water bodies), was selected to investigate the ecological processes of microbial communities and N- and P-transformation processes in multistage ditches. We found that scale effects drove distinct environmental gradients and microbial community dissimilarities and that the five ordered ditches were grouped into three clusters (field vs. sublateral vs. head, branch, and trunk ditches). Specifically, the microbial communities in the field ditches located adjacent to the paddy fields were strongly selected by agricultural fertilization and irrigation drainage, enriching salt-tolerant microbes with high nitrification and inorganic P solubilization capabilities. In comparison, the sublateral ditches showed the highest removal performance for total nitrogen (13.28-55.80%) and total phosphorus (9.06-65.07%) during the growth of rice, which was mainly attributed to the enrichment of versatile microbiota (e.g., C39, Nitrospira, and Novosphingobium) as a result of the increased stochastic processes driven by the low redox potential. Notably, the specific gene (i.e., hzsB) for anaerobic ammonium oxidation in sublateral ditches was 1-2 orders of magnitude higher than in adjacent ditches, further contributing to N loss. As field water was discharged into the large-sized head, branch, and trunk ditches, the nutrient levels decreased sharply. At the same time, deterministic processes gained more importance (∼82%), leading to the flourishing of Synechococcus and increasing the potential risk of eutrophication. Overall, the microbial communities in multistage ADDs were co-shaped by agricultural practices and ditch size, which further governed the N and P removal performance. These results provide unique insights into microbiota assembly patterns and dynamics in multistage ADDs and important ecological knowledge for controlling agricultural non-point source pollutants by managing of small-sized ditches.

Nitrate input inhibited the biodegradation of erythromycin through affecting bacterial network modules and keystone species in lake sediments.

Antibiotic contamination and excessive nitrate loads are generally concurrent in aquatic ecosystems. However, little is known about the effects of nitrate input on the biodegradation of antibiotics. In this study, the effects of nitrate input on microbial degradation of erythromycin, a typical macrolide antibiotic widely detected in lake sediments, were investigated. The results showed that the nitrate input significantly inhibited the erythromycin removal and such an inhibitory effect was strengthened with the increased input dosages. Nitrate input significantly increased sediment nitrite concentration, indicating enhanced denitrification under high nitrate pressure. Bacterial network module and keystone species analysis showed that nitrate input enriched the keystone species involved in denitrification (e.g., Simplicispira and Denitratisoma). In contrast, some potential erythromycin-degrading bacteria (e.g., Desulfatiglandales, Pseudomonadales, Nitrospira) were inhibited by nitrate input. The variations in dominant bacterial groups implied competition between denitrification and erythromycin degradation in response to nitrate input. Based on the partial least squares path modeling analysis, keystone species (total effect: 0.419) and bacterial module (total effect: 0.403) showed strong association with erythromycin removal percentage. This indicated that the inhibitory effect of nitrate input on erythromycin degradation was mainly explained by bacterial network modules and keystone species. These findings will help us to assess the bioremediation potential of antibiotic-contaminated sediments suffering from excessive nitrogen discharge concurrently.

Triggering Dual Two-electron Pathway for H2 O2 Generation by Multiple [Bi-O]n Interlayers in Ultrathin Bi12 O17 Cl2 towards Efficient Piezo-self-Fenton Catalysis.

Piezo-self-Fenton system (PESF) has been emerging as a promising water treatment technology but suffering from unsatisfied H2 O2 production efficiency. Herein, we rationally design a Bi12 O17 Cl2 piezo-catalyst with multiple [Bi-O]n interlayers towards highly efficient H2 O2 production. The introduction of [Bi3 O4.25 ] layers initiates dual two-electron pathway for H2 O2 generation by altering the interlayer properties. It is found that the additional [Bi3 O4.25 ] layers not only enhance the polarization electric field but also serve as active sites for triggering dual pathways of two-electron O2 reduction and H2 O oxidation reaction for H2 O2 production. Therefore, the Bi12 O17 Cl2 exhibits an ultrahigh rate of H2 O2 generation (7.76 mM h-1 g-1 ) in pure water. Based on the adequate H2 O2 yield, a PESF was constructed for acetaminophen (ACE) degradation with an apparent rate constant of 0.023 min-1 . This work not only presents a potential strategy of tuning the activity of bismuth based piezo-catalysts but also provides a good example on the construction of highly efficient PESF for environmental remediation by using natural mechanical energy.

Gastrointestinal Degradation and Toxicity of Disinfection Byproducts in Drinking Water Using In Vitro Models and the Roles of Gut Microbiota.

Disinfection byproducts (DBPs) in drinking water are mainly exposed to the human body after oral ingestion and degradation in the gastrointestinal tract. The role of gastrointestinal degradation in the toxic effects of DBPs still needs further investigation. In this study, the degradation of five categories of DBPs (22 DBPs) in the stomach and small intestine was investigated based on a semicontinuous steady-state gastrointestinal simulation system, and 22 DBPs can be divided into three groups based on their residual proportions. The degradation of chloroacetonitrile (CAN), dibromoacetic acid (DBAA), and tetrabromopyrrole (FBPy) was further analyzed based on the Simulator of the Human Intestinal Microbial Ecosystem inoculating the gut microbiota, and approximately 60% of CAN, 45% of DBAA, and 80% of FBPy were degraded in the stomach and small intestine, followed by the complete degradation of remaining DBPs in the colon. Meanwhile, gastrointestinal degradation can reduce oxidative stress-mediated DNA damage and apoptosis induced by DBPs in DLD-1 cells, but the toxicity of DBPs did not disappear with the complete degradation of DBPs, possibly because of their interferences on gut microbiota. This study provides new insights into investigating the gastrointestinal toxic effects and mechanisms of DBPs through oral exposure.

Metagenomic insight into the distribution of metal resistance genes within cascade reservoir waters: Synergic impacts of geographic variation and anthropogenic pollution.

Metal resistance genes (MRGs) are potential bio-indicators to diagnose contamination stress on riverine ecosystems. Within reservoir systems, river damming weakens hydrodynamic condition and enriches metal contaminants. But, little is known about the synergic impacts of geographic variation and anthropogenic pollution on MRGs. In this study, the abundance, composition and microbes of MRGs in four cascade reservoirs along the Jinsha River, southwestern China were investigated via high-throughput metagenomics. The results showed significant enrichment of chromium, cadmium and lead in Ludila and Xiluodu reservoirs with moderate ecological risks based on the criteria of drinking water quality and aquatic life protection. Nevertheless, at watershed scale, these metals played little role in up-regulating MRGs abundance owing to the limited toxic stress on microbes. Accordingly, geographic variation showed stronger impacts on MRGs composition than metals as revealed by the distance-decay relationship (Pearson correlation, rgeo = 0.24-0.57, rmetal = 0.10-0.41) and co-occurrence network (Node degree to MRGs subtype, ngeo = 180, nmetal = 6). River damming, as an artificial isolation of geographic space, significantly affected MRGs composition. The longer operation history, smaller storage capacity and higher regulation frequency caused the higher dissimilarity of MRGs composition between the reservoir's upstream and downstream areas. In conclusion, the metal pollution level is a prerequisite regulating MRGs; while under the lowly-polluted conditions, geographic variation had stronger impacts on MRGs than metal pollution via altered assembly of microbial communities. This study provides an important guidance for the future environmental management and ecological protection of river-reservoir ecosystems.

Highly Efficient FeIII -initiated Self-cycled Fenton System in Piezo-catalytic Process for Organic Pollutants Degradation.

Piezo-catalytic self-Fenton (PSF) system has been emerging as a promising technique for wastewater treatment, while the competing O2 reductive hydrogen peroxide (H2 O2 ) production and FeIII reduction seriously limited the reaction kinetics. Here, we develop a two-electron water oxidative H2 O2 production (WOR-H2 O2 ) coupled with FeIII reduction over a FeIII /BiOIO3 piezo-catalyst for highly efficient PSF. It is found that the presence of FeIII can simultaneously initiate the WOR-H2 O2 and reduction of FeIII to FeII , thereby enabling a rapid reaction kinetics towards subsequent Fenton reaction of H2 O2 /FeII . The FeIII initiating PSF system offers exceptional self-recyclable degradation of pollutants with a degradation rate constant for sulfamethoxazole (SMZ) over 3.5 times as that of the classic FeII -PSF system. This study offers a new perspective for constructing efficient PSF systems and shatters the preconceived notion of FeIII in the Fenton reaction.

Light-driven Orderly Assembly of Ir-atomic Chains to Integrate a Dynamic Reaction Pathway for Acidic Oxygen Evolution.

This work suggests an intriguing light-driven atomic assembly proposal to orderly configure the distribution of reactive sites to optimize the spin-entropy-related orbital interaction and charge transfer from electrocatalysts to intermediates. Herein, the introduced fluorine (F) atoms acting as photo-corrosion centres in MnO1.9 F0.1 effectively soften the bonding interaction of Mn-O bonds in the IrCl3 solution. Therefore, partial Mn atoms can be successively replaced to form orderly atomic-hybridized catalysts with a spin-related low entropy due to the coexistence of Ir-atomic chains and clusters. The time-related elemental analysis demonstrates that the dynamic dissolution/redeposition of Ir clusters in acidic oxygen evolution leads to a reintegration of the reaction pathway to seek the switchable rate-limiting step with a lower activation energy.

A novel procedure for predicting chronic toxicities and ecological risks of perfluorinated compounds in aquatic environment.

Perfluorinated compounds (PFCs) can pose adverse effect on aquatic species and community structure. However, little is known about how the characteristics of molecules of PFCs affect their chronic toxic potencies to aquatic species, and the species sensitivity distributions (SSDs) and ecological risk assessments of PFCs are hampered by limited available data of chronic toxicity. In the present study, a novel procedure is proposed to obtain the ecological risk of PFCs using existing exposure concentrations of PFCs and SSDs integrated with the chronic toxicity prediction through robust QSAR models. The results showed that the energy of the lowest unoccupied molecular orbital (ELUMO) exhibited the strongest correlation with the chronic toxicities of 15 PFCs (R2 > 0.844, F > 16.206, p < 0.05). SSDs of 15 PFCs on eight species were first constructed, and the SSD fitting parameters were significantly correlated with ELUMO (R2 > 0.610, F > 19.471, p < 0.05). The QSAR-SSDs support the evaluation of hazardous criteria of PFCs for which data are lacking. Given environmental exposure distributions (EEDs) of the national presence of PFCs in aquatic systems in China, the QSAR-SSDs models allow the development of the ecological risk assessment for PFCs. This way, it was concluded that negligible environmental risk (defined as 5% of the species being potentially exposed to concentrations able to cause effects in < 5% of the case) could be expected from exposure to PFCs in surface waters in China. This method may be helpful for providing an evidence-based approach to guide the risk management for PFCs in aquatic environment.

How dam construction affects the activity of alkaline phosphatases in reservoir sediments: A study of two highly regulated rivers.

Dam construction causes phosphorus (P) accumulation in reservoir sediments and significantly affects the generation of available P. However, the effect of dam construction on the activity of sediment alkaline phosphatase (ALP), which is encoded by the bacterial phoD gene and participates in P mineralization, in river sediments remains unclear. Here, we investigated the ALP activities in 78 sediment samples collected from the cascade reservoir regions located in the Lancang River and the Jinsha River, two highly regulated rivers in southwestern China. The abundance and community composition of phoD-harboring bacteria were determined based on the phoD gene using quantitative real-time PCR and MiSeq sequencing, respectively. Comparison of control and affected sites indicated that dam construction significantly increased sediment ALP activity in both rivers. The abundances of phoD-harboring bacteria increased and their community compositions varied in response to dam construction; the relative abundances of the dominant genera Methylobacterium and Bradyrhizobium were particularly higher in affected site than control site. Co-occurrence network analyses revealed much higher network connectivity and relative abundances of keystone species in affected sites. Some microbial factors including phoD-harboring bacterial abundances, network clustering coefficients, and relative abundance of keystone species were positively correlated with ALP activity. The relative abundance of keystone species was identified as the most important microbial factor contributing to variation in ALP activity based on structural equation modeling analysis. These findings enhance our understanding of how dam construction affects the functions of phoD-harboring bacteria and their role in the P biogeochemical cycle in highly regulated rivers.

Covalent-anion-driven self-assembled cadmium/ molybdenum sulfide hybrids for efficient nitenpyram degradation.

Photocatalytic technology is an attractive and promising approach for nitenpyram degradation; however, how to ensure the carrier separation efficiency and catalytic sites exposure is still great challenges. In this study, we construct CdS@MoS2 (CM) nanohybrids with a 3D hierarchical configuration to enhance the separation and transfer efficiency of the photo-induced electron by a covalent-anion-driven self-assembly method. The vertical orientation of MoS2 ultrathin nanosheets not only provides a large specific surface area for the oxidation and reduction reactions but also enables the active edge sites of MoS2 to be maximally exposed. As a result, this structure drastically facilitates the exposure of the catalytic active region and the performance of the carrier transfer and injection into photocatalytic degradation for nitenpyram (NTP). The optimal CdS-MoS2 has an impressive and stable NTP removal efficiency with a high reaction rate constant up to 0.078 min-1, which is 3.25 times higher than that of pure cadmium sulfide. The photocatalytic degradation mechanism and degradation pathway of NTP were presented by synthesizing the results of experimental analysis and density flooding theory (DFT) calculations. In further, for the first time, the cytotoxicity and genotoxicity of NTP on moving bed biofilm reactors (MBBRs) was disclosed and a continuous photocatalytic wastewater pretreatment device based on the CM is proposed for the stable biological nitrogen removal activity of MBBRs, which can degrade more than 80% NTP per hour.

Recharged Catalyst with Memristive Nitrogen Reduction Activity through Learning Networks of Spiking Neurons.

Electrocatalysis from N2 to NH3 has been increasingly studied because it provides an environmentally friendly avenue to take the place of the current Haber-Bosch method. Unfortunately, the conversion of N2 to NH3 is far below the necessary level for implementation at a large scale. Inspired by signal memory in a spiking neural network, we developed rechargeable catalyst technology to activate and remember the optimal catalytic activity using manageable electrical stimulation. Herein, we designed double-faced FeReS3 Janus layers that mimic a multiple-neuron network consisting of resistive switching synapses, enabling a series of intriguing multiphase transitions to activate undiscovered catalytic activity; the activation energy barrier is clearly reduced via an active site conversion between two nonequivalent surfaces. Electrical field-stimulated FeReS3 demonstrates a Faradaic efficiency of 43% and the highest rate of 203 µg h-1 mg-1 toward NH3 synthesis. Moreover, this rechargeable catalyst displays unprecedented catalytic performance that persists for up to 216 h and can be repeatedly activated through a simple charging operation.

Anthropogenic disturbances on distribution and sources of pharmaceuticals and personal care products throughout the Jinsha River Basin, China.

Pharmaceuticals and personal care products (PPCPs) are recognized as a group of emerging contaminants closely related to anthropogenic activities, which capture increasing attention worldwide. To evaluate the anthropogenic disturbances on PPCP distribution and sources, this study investigated the distribution and sources of 50 PPCPs along the 2300 km long Jinsha River and revealed different anthropogenic disturbances on PPCPs. Results showed that 40 out of the 50 PPCPs were ubiquitously detected among these river water samples, with the concentrations varied from less than 1 ng/L to more than 500 ng/L. Although most PPCPs concentrations were much lower in the Jinsha River than in highly developed rivers, the prevalence of PPCPs suggested the widespread use and improper disposal of PPCPs in the Jinsha River. The risk assessment also revealed that some PPCPs posed risks to aquatic organisms in the Jinsha River. Anthropogenic activities including human habitation and dam construction had different influence on PPCPs. PPCP distribution varied significantly across the "Hu Huanyong line", indicating human habitation significantly influenced PPCP distribution. Dam construction was insignificant in altering PPCP distribution throughout the Jinsha River. Moreover, the land use index indicated degradation level of multiple lands related to anthropogenic activities and represented the major sources of PPCPs in the Jinsha River. Most PPCPs were correlated with anthropogenic lands, for example, antibiotics, analgesics, and endocrine disrupting chemicals mainly originated from artificial surfaces, whereas other PPCPs mainly originated from cultivated lands. Together, this study indicates the disturbances of multiple anthropogenic activities on PPCP distribution and sources along the Jinsha River, which contributes to PPCP management in rural areas.

Distinct strategies of abundant and rare bacterioplankton in river-reservoir system: Evidence from a 2800 km plateau river.

Riverine bacterioplankton are highly responsive to river alterations and their abundant and rare sub-communities may have different roles in biogeochemical cycling. However, with the rapid development of dam constructions, our knowledge on adaptation mechanism of these sub-communities in regulated river ecosystem was still limited, especially with regard to their functional traits. Here, our study was conducted in the 2800 km Yarlung Tsangpo River on the Tibetan Plateau to address the question of how abundant and rare bacterioplankton would respond taxonomically and functionally to river damming using 16S rRNA gene sequencing combined with Geochip microarray technique. Our results showed that abundant sub-community dominated taxonomic composition while rare sub-community largely determined functional composition. It is also observed that taxonomic diversity of abundant sub-community was significantly stimulated in the reservoir while that of rare sub-community was markedly inhibited. Moreover, abundant sub-community exhibited functional redundancy under damming disturbances since altered taxonomic composition and unaltered functional composition co-occurred simultaneously. Meanwhile, due to portfolio effect, rare sub-community maintained a greater stability under damming disturbances with little variation in taxonomic and functional compositions. In addition, the Stegen null model analysis revealed that stochastic process governed community assembly in both abundant and rare sub-communities. However, according to source tracking analysis, the taxonomic dispersion of abundant sub-community was less significantly impeded by the dam while the functional dispersion of rare sub-community was less strongly interrupted, indicating that the dispersal process in the dominated sub-community was less susceptible to damming. Therefore, by considering bacterioplankton functional traits, our study provided comprehensive evidences for the distinct strategies of abundant and rare sub-communities in response to damming.

Perfluorooctanoic Acid (PFOA) and Perfluorooctanesulfonic Acid (PFOS) in Surface Water of China: National Exposure Distributions and Probabilistic Risk Assessment.

This study presents a comprehensive application of the probabilistic risk assessment methodology for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), which are two types of perfluoroalkyl acids frequently studied in recent years. The exposure characteristics of PFOA and PFOS in Chinese surface water on a nationwide scale were summarized. Individual predicted no-effect concentration (PNEC) and the sensitivities for taxonomic groups of primary producers, invertebrates, and vertebrates were derived by the species sensitivity distributions method. Both hazard quotients (HQs) and joint probability curves were calculated to assess the risks to aquatic organisms. Among seven Chinese river basins, the mean concentrations of PFOA and PFOS in the Yangtze River Basin were the highest (58 ng/L and 22 ng/L, respectively), while the lowest concentrations (< 1 ng/L) were in the Songhua River Basin. The acute PNEC value was 2.43 mg/L for PFOA and 0.96 mg/L for PFOS, and the chronic PNEC value was 0.0067 mg/L for PFOA and 0.0012 mg/L for PFOS, respectively. The sensitivities of different taxonomic groups revealed higher sensitivity of primary producers for PFOA and higher sensitivity of invertebrates for PFOS. The acute HQs of PFOA and PFOS were less than 1. The probabilities of exposure concentrations exceeding 5th percentile toxicity value of the chronic data for all aquatic organisms were 1.65% for PFOA and 1.23% for PFOS, respectively, suggesting a low probability of effects to aquatic organisms. Compared with the risk scenarios worldwide, the ecological risks for chronic effects decreased in the order of PFOS (worldwide) > PFOA (China) > PFOS (China) > PFOA (worldwide).

Mechanisms of photochemical release of dissolved organic matter and iron from resuspended sediments.

Photochemical reactions can alter the transformation of sedimentary organic matter into dissolved organic matter (DOM) and affect its ultimate fate in water ecosystems. In the present study, the photorelease of DOM and Fe from resuspended lake sediments was investigated under different O2 and NO3- concentration conditions to study the mechanisms of DOM and Fe photorelease. The amount of photoreleased Fe, which ranged from 0.22 to 0.70 µmol/L, was significantly linearly correlated with the amount of photoreleased DOM. O2 and NO3- could promote the photochemical release of DOM and Fe, especially during the initial 4 h irradiation. In general, the order of the photorelease rates of DOM and Fe under different conditions was as follows: NO3-/aerobic > aerobic ≈ NO3-/anaerobic > anaerobic. The photorelease rates of DOM and Fe were higher for the initial 4 hr irradiation than these for the subsequent 8 hr irradiation. The photorelease of DOM and Fe is thought to proceed via direct photodissolution and indirect processes. The relative contributions of indirect processes (>60%) was much greater than that of direct photodissolution (<40%). The photoproduced H2O2 under aerobic and anaerobic conditions indicated that hydroxyl radicals (•OH) are involved in the photorelease of DOM. Using •OH scavengers, it was found that 38.7%, 53.7%, and 77.6% of photoreleased DOM was attributed to •OH under anaerobic, aerobic, and NO3-/aerobic conditions, respectively. Our findings provide insights for understanding the mechanisms and the important role of •OH in the DOM and Fe photorelease from resuspended sediments.

Iodide-Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High-Performance Quasi-Homogeneous Photocatalytic H2 O2 Production.

Polymeric carbon nitride (PCN) as a class of two-electron oxygen reduction reaction (2 e- ORR) photocatalyst has attracted much attention for H2 O2 production. However, the low activity and inferior selectivity of 2 e- ORR greatly restrict the H2 O2 production efficiency. Herein, we develop a new strategy to synthesize hydrophilic, fragmented PCN photocatalyst by the terminating polymerization (TP-PCN) effect of iodide ions. The obtained TP-PCN with abundant edge active sites (AEASs), which can form quasi-homogeneous photocatalytic system, exhibits superior H2 O2 generation rate (3265.4 µM h-1 ), far surpassing PCN and other PCN-based photocatalysts. DFT calculations further indicate that TP-PCN is more favorable for electron transiting from ß spin-orbital to the π* orbitals of O2 , which optimizes O2 activation and reduces the energy barrier of H2 O2 formation. This work provides a new concept for designing functional photocatalysts and understanding the mechanism of O2 activation in ORR for H2 O2 production.

Fungal community demonstrates stronger dispersal limitation and less network connectivity than bacterial community in sediments along a large river.

Despite the essential functions of sedimentary bacterial and fungal communities in biogeochemical cycling, little is known about their biogeographic patterns and driving processes in large rivers. Here we investigated the biogeographic assemblies and co-occurrence patterns of sedimentary bacterial and fungal communities in the Jinsha River, one of the largest rivers in southwestern China. The mainstream of river was divided into upstream, midstream and downstream. The results showed that both bacterial and fungal communities differed significantly among three sections. For both communities, their composition variations in all sites or each river section were controlled by the combination of dispersal limitation and environmental selection, and dispersal limitation was the dominant factor. Compared with bacteria, fungi had stronger dispersal limitation. Co-occurrence network analyses revealed higher network connectivity but a lower proportion of positive interaction in the bacterial than fungal network at all sites. In particular, the keystone species belonging to bacterial phyla Proteobacteria and Firmicutes and fungal phyla Ascomycota and Chytridiomycota may play critical roles in maintaining community function. Together, these observations indicate that fungi have a stronger dispersal limitation influence and less network connectivity than bacteria, implying different community assembly mechanisms and ecological functions between bacteria and fungi in large rivers.