Unveiling Microbial Nitrogen Metabolism in Rivers using a Machine Learning Approach.

Microbial nitrogen metabolism is a complicated and key process in mediating environmental pollution and greenhouse gas emissions in rivers. However, the interactive drivers of microbial nitrogen metabolism in rivers have not been identified. Here, we analyze the microbial nitrogen metabolism patterns in 105 rivers in China driven by 26 environmental and socioeconomic factors using an interpretable causal machine learning (ICML) framework. ICML better recognizes the complex relationships between factors and microbial nitrogen metabolism than traditional linear regression models. Furthermore, tipping points and concentration windows were proposed to precisely regulate microbial nitrogen metabolism. For example, concentrations of dissolved organic carbon (DOC) below tipping points of 6.2 and 4.2 mg/L easily reduce bacterial denitrification and nitrification, respectively. The concentration windows for NO3--N (15.9-18.0 mg/L) and DOC (9.1-10.8 mg/L) enabled the highest abundance of denitrifying bacteria on a national scale. The integration of ICML models and field data clarifies the important drivers of microbial nitrogen metabolism, supporting the precise regulation of nitrogen pollution and river ecological management.

Ensemble learning model identifies adaptation classification and turning points of river microbial communities in response to heatwaves.

Heatwaves are a global issue that threaten microbial populations and deteriorate ecosystems. However, how river microbial communities respond to heatwaves and whether and how high temperatures exceed microbial adaptation remain unclear. In this study, we proposed four types of pulse temperature-induced microbial responses and predicted the possibility of microbial adaptation to high temperature in global rivers using ensemble machine learning models. Our findings suggest that microbial communities in parts of South American (e.g., Brazil and Chile) and Southeast Asian (e.g., Vietnam) countries are likely to change due to heatwave disturbance from 25 to 37°C for consecutive days. Furthermore, the microbial communities in approximately 48.4% of the global river gauge stations are prone to fast stress inadaptation, with approximately 76.9% of these stations expected to exceed microbial adaptation after heatwave disturbances. If emissions of particulate matter with sizes not more than 2.5 µm (PM2.5, an indicator of human activities) increase by twofold, the number of global rivers associated with the fast stress adaptation type will decrease by ~13.7% after heatwave disturbances. Understanding microbial responses is crucially important for effective ecosystem management, especially for fragile and sensitive rivers facing heatwave events.

DOM Associates with Greenhouse Gas Emissions in Chinese Rivers under Diverse Land Uses.

Growing evidence indicates that rivers are hotspots of greenhouse gas (GHG) emissions and play multiple roles in the global carbon budget. However, the roles of terrestrial carbon from land use in river GHG emissions remain largely unknown. We studied the microbial composition, dissolved organic matter (DOM) properties, and GHG emission responses to different landcovers in rivers (n = 100). The bacterial community was mainly constrained by land-use intensity, whereas the fungal community was mainly controlled by DOM chemical composition (e.g., terrestrial DOM with high photoreactivity). Anthropogenic stressors (e.g., land-use intensity, gross regional domestic product, and total population) were the main factors affecting chromophoric DOM (CDOM). DOM biodegradability exhibited a positive correlation with CDOM and contributed to microbial activity for DOM transformation. Variations in CO2 and CH4 emissions were governed by the biodegradation or photomineralization of dissolved organic carbon derived from autotrophic DOM and were indirectly affected by land use via changes in DOM properties and water chemistry. Because the GHG emissions of rivers offset some of the climatic benefits of terrestrial carbon (or ocean) sinks, intensified urban land use inevitably alters carbon cycling and changes the regional microclimate.

Potential contribution of chlorella vulgaris to carbon-nitrogen turnover in freshwater ecosystems after a great sandstorm event.

Urban lakes represent important land-water and nature-human dual interfaces that promote the cycling of elements from terrestrials to sediments and consequently modulating the stabilization of regional climate. However, whether disturbances caused by extreme weather events can have substantial effects on carbon-nitrogen (C-N) cycling in these ecosystems are vague. To explore the impact of phytoplankton on the ecological retention time of C-N, two kinds of freshwater (natural and landscape) were collected and conducted a microcosm experiment using a freshwater algal species Chlorella vulgaris. Sandstorm events increased dissolved inorganic carbon in freshwater (65.55 ± 3.09 and 39.46 ± 2.51 mg·L-1 for samples from Jinyang and Nankai, respectively) and significantly affected the relevant pathways of photosynthesis in Chlorella vulgaris, including enhancing chlorophyll fluorescence (The effective quantum yield of PSII at the fifth day of incubation was 0.34 and 0.35 for Nankai and Jinyang, respectively), promoting the synthesis of sugars and inhibiting the synthesis of glycine and serine related proteins. Besides, carbon from plant biomass accumulation and cellular metabolism (fulvic acid-like, polyaromatic-type humic acid and polycarboxylate-type humic acid, etc.) was enriched into residues and become a kind of energy source for the decomposer (TC mass increased by 1.63-2.13 times after 21 days of incubation). This means that the accumulation and consumption of carbon and nitrogen in the residue can be used to track the processes controlling the long-term C-N cycle. Our findings shed light on the plant residues were key factors contributing to the formation of water carbon pool, breaks the traditional theory that dissolved carbonates cannot produce carbon sinks.

Combined effects of microplastics and warming enhance algal carbon and nitrogen storage.

Algae dominate primary production in groundwater and oceans and play a critical role in global carbon dioxide fixation and climate change but are threatened by ongoing global warming events (such as heatwaves) and increasing microplastic (MP) pollution. However, whether and how ecologically important phytoplankton respond to the combined effects of warming and MPs remain poorly understood. We thus investigated the combined effects of these factors on carbon and nitrogen storage and the mechanisms underlying the alterations in the physiological performance of a model diatom, Phaeodactylum tricornutum, exposed to a warming stressor (25 °C compared with 21 °C) and polystyrene MP acclimation. Although warmer conditions decreased the cell viability, the diatoms subjected to the synergistic effects of MPs and warming showed significant increases in the growth rate (1.10-fold) and nitrogen uptake rate (1.26-fold). Metabolomics and transcriptomic analyses revealed that MPs and warming mainly promoted fatty acid metabolism, the urea cycle, glutamine and glutamate production, and the tricarboxylic acid (TCA) cycle due to an increased level of 2-oxoglutarate, which is the hub of carbon and nitrogen metabolism and accounts for the acquisition and utilization of carbon and nitrogen. Our findings emphasize the nonnegligible effects of MPs and HWs on the algal carbon and nitrogen cycles in waters.

Microplastics trigger the Matthew effect on nitrogen assimilation in marine diatoms at an environmentally relevant concentration.

Microplastics (MPs, diameter <5 mm) are widely distributed on Earth, especially in the oceans. Diatoms account for ∼40% of marine primary productivity and affect the global biogeochemical cycles of macroelements. However, the effects of MPs on marine nitrogen cycling remain poorly understood, particularly comparisons between nitrogen-replete and nitrogen-limited conditions. We found that MPs trigger the Matthew effect on nitrogen assimilation in diatoms, where MPs inhibited nitrogen assimilation under nitrogen-limited conditions while enhancing nitrogen metabolism under nitrogen-replete conditions in Phaeodactylum tricornutum. Nitrate reductase (NR) and nitrite reductase (NIR) are upregulated, but nitrate transporter (NRT) and glutamine synthetase (GS) are downregulated by MPs under nitrogen-limited conditions. In contrast, NR, NIR, and GS are all upregulated by MPs under nitrogen-replete conditions. MPs accelerate nitrogen anabolic processes with an increase in the accumulation of carbohydrates by 80.7 ± 7.9% and enhance the activities of key nitrogen-metabolizing enzymes (8.20-44.90%) under nitrogen-replete conditions. In contrast, the abundance of carbohydrates decreases by 22.0-34.4%, and NRT activity is inhibited by 79.0-86.5% in nitrogen-limited algae exposed to MPs. Metabolomic and transcriptomic analyses were performed to further explore the molecular mechanisms of reprogrammed nitrogen assimilation, including carbon metabolism, nitrogen transport and ammonia assimilation. The aforementioned spatial redistribution (e.g., the Matthew effect between nitrogen-replete and -limited conditions) of nitrogen assimilation highlights the potential risks of MP contamination in the ocean.

Interactions between dissolved organic matter and the microbial community are modified by microplastics and heat waves.

Dissolved organic matter (DOM) exists widely in natural waters and plays an important role in river carbon cycles and greenhouse gas emissions through microbial interactions. However, information on DOM-microbe associations in response to environmental stress is limited. River environments are the main carriers of microplastic (MP) pollution, and global heat waves (HWs) are threatening river ecology. Here, through MP exposure and HW simulation experiments, we found that DOM molecular weight and aromaticity were closely related to initial microbial communities. Moreover, MP-derived DOM regulated microbial community abundance and diversity, influenced microorganism succession trajectories as deterministic factors, and competed with riverine DOM for microbial utilization. SimulatedHWs enhanced the MP-derived DOM competitive advantage and drove the microbial community to adopt a K-strategy for effective recalcitrant carbon utilization. Relative to single environmental stressor exposure, combined MP pollution and HWs led to a more unstable microbial network. This study addresses how MPs and HWs drive DOM-microbe interactions in rivers, contributes to an in-depth understanding of the fate of river DOM and microbial community succession processes, and narrows the knowledge gap in understanding carbon sinks in aquatic ecosystems influenced by human activities and climate change.

Enhanced carbon emission driven by the interaction between functional microbial community and hydrocarbons: An enlightenment for carbon cycle.

Soil microbial communities are usually regarded as one of the key players in the global element cycling. Moreover, an important consequence of oil contamination altering the structure of microbial communities is likely to result in an increased carbon emission. However, understanding of the complex interactions between environmental factors and biological communities is clearly lagging behind. Here it showed that the flux of carbon emissions increased in oil-contaminated soils, up to 13.64 g C·(kg soil)-1·h-1. This phenomenon was mainly driven by the enrichment of rare degrading microorganisms (e.g., Methylosinus, Marinobacter, Pseudomonas, Alcanivorax, Yeosuana, Halomonas and Microbulbifer) in the aerobic layer, rather than the anaerobic layer, which is more conducive to methane formation. In addition, petroleum hydrocarbons and environmental factors are equally important in shaping the structure of microbial communities (the ecological stability) and functional traits (e.g., fatty acid metabolism, lipid metabolism and amino acid metabolism) due to the different ecological sensitivities of microorganisms. Thus, it can be believed that the variability of rare hydrocarbon degrading microorganisms is of greater concern than changes in dominant microorganisms in oil-contaminated soil. Undoubtedly, this study could reveal the unique characterization of bacterial communities that mediate carbon emission and provide evidence for understanding the conversion from carbon stores to carbon gas release in oil-contaminated soils.

Dual regulatory effects of microplastics and heat waves on river microbial carbon metabolism.

Rivers play a critical role in the global carbon cycle, but the processes can be affected by widespread microplastic (MP) pollution and the increasing frequency of heat waves (HWs) in a warming climate. However, little is known about the role of river microbes in regulating the carbon cycle under the combined action of MP pollution and HWs. Here, through seven-day MP exposure and three cycles of HW simulation experiments, we found that MPs inhibited the thermal adaptation of the microbial community, thus regulating carbon metabolism. The CO2 release level increased, while the carbon degradation ability and the preference for stable carbon were inhibited. Metabonomic, 16 S rRNA and ITS gene analyses further revealed that the regulation of carbon metabolism was closely related to the microbial r-/K- strategy, community assembly and transformation of keystone taxa. The random forest model revealed that dissolved oxygen and ammonia-nitrogen were important variables influencing microbial carbon metabolism. The above findings regarding microbe-mediated carbon metabolism provide insights into the effect of climate-related HWs on the ecological risks of MPs.

Efficient electro-catalyzed PMS activation on a Fe-ZIF-8 based BTNAs/Ti anode: An in-depth investigation on anodic catalytic behavior.

Phenanthrene (PHE), mainly released from coal tar and petroleum distillation, is an important kind of prevalent polycyclic aromatic hydrocarbons (PAHs) contamination in China (up to 2.38 ± 0.02 mg/kg in soil and 8668 ng/L in surface water) and other countries in the world. Metal-organic frameworks (MOFs) show promising application prospects in the decontamination field, however, suffering from the intrinsic fragility and fine powder forms. Therefore, macroscopic MOFs architecture-sandwich-like Fe-ZIF-8/blue TiO2 nanotube arrays (BTNAs)/Ti substrate (FBTT) anode with strong interfacial bonding (Fe-O-Ti and Fe-2-MIM-Ti coordination) was constructed using innovative in situ growth, condensation-crystallization-deposition, and pyrolysis methods, aiming at exploring the feasibility of MOFs-based anode/peroxymonosulfate (PMS) mediated PHE elimination, revealing the in-depth mechanisms, simultaneously overcoming the intrinsic drawbacks of MOFs. The FBTT-4 (doping content of 30 %) efficiently degraded PHE by 90.01 % and 74.5 % within 10 min at 350 µg/L and 3 mg/L, respectively, mediated by the ·OH compared to the SO4·-, 1O2, and O2·-. Post-optimized range of anodic potential enabled (i) anodic oxidation, (ii) activation of water and PMS molecules to produce active species, (iii) capture of electrons in reactants to reduce Fe3+/Ti4+ to Fe2+/Ti3+, maintaining the proportion of Fe/Ti with low valence and thus stable PMS activation capacity, and (iv) regulation of the Fe/Ti d-band center to modulate the anode adsorption capacity. The further increment in anodic potential could promote "dark photocatalysis" with a Z-scheme-like mechanism. Thus, it is proposed that the development of macroscopic MOFs-based anode, especially those with small band gaps, represents vast potentials in electrocatalytic contamination elimination. Simultaneously, the MOFs-based anode is expected to fully exploit their catalytic capacities and solve their intrinsic defects as well.

Marine Colloids Promote the Adaptation of Diatoms to Nitrate Contamination by Directional Electron Transfer.

Nitrate contamination from human activities (e.g., domestic pollution, livestock breeding, and fertilizer application) threatens marine ecosystems and net primary productivity. As the main component of primary productivity, diatoms can adapt to high nitrate environments, but the mechanism is unclear. We found that electron transfer from marine colloids to diatoms enhances nitrogen uptake and assimilation under visible-light irradiation, providing a new pathway for nitrogen adaptation. Under irradiation, marine colloids exhibit semiconductor properties (e.g., the separation of electron-hole pairs) and can trigger the generation of free electrons and singlet oxygen. They also exhibit electron acceptor and donor properties, with the former being stronger than the latter, reacting with polysaccharides in extracellular polymeric substances (EPSs) under high nitrogen stress, enhancing the elasticity and permeability of cells, and promoting nitrogen assimilation and electron transfer to marine diatom EPSs. Electron transfer promotes extracellular-to-intracellular nitrate transport by upregulating membrane nitrate transporters and nitrate reductase. The upregulation of anion transport genes and unsaturated fatty acids contributes to nitrogen assimilation. We estimate that colloids may increase the nitrate uptake efficiency of marine diatoms by 10.5-82.2%. These findings reveal a mechanism by which diatoms adapt to nitrate contamination and indicate a low-cost strategy to control marine pollution.

Study of the Persistence of the Phytotoxicity Induced by Graphene Oxide Quantum Dots and of the Specific Molecular Mechanisms by Integrating Omics and Regular Analyses.

Although increasing attention has been paid to the nanotoxicity of graphene oxide quantum dots (GOQDs) due to their broad range of applications, the persistence and recoverability associated with GOQDs had been widely ignored. Interestingly, stress-response hormesis for algal growth was observed for Chlorella vulgaris as a single-celled model organism. Few physiological parameters, such as algal density, plasmolysis, and levels of reactive oxygen species, exhibited facile recovery. In contrast, the effects on chlorophyll a levels, permeability, and starch grain accumulation exhibited persistent toxicity. In the exposure stage, the downregulation of genes related to unsaturated fatty acid biosynthesis, carotenoid biosynthesis, phenylpropanoid biosynthesis, and binding contributed to toxic effects on photosynthesis. In the recovery stage, downregulation of genes related to the cis-Golgi network, photosystem I, photosynthetic membrane, and thylakoid was linked to the persistence of toxic effects on photosynthesis. The upregulated galactose metabolism and downregulated aminoacyl-tRNA biosynthesis also indicated toxicity persistence in the recovery stage. The downregulation and upregulation of phenylalanine metabolism in the exposure and recovery stages, respectively, reflected the tolerance of the algae to GOQDs. The present study highlights the importance of studying nanotoxicity by elucidation of stress and recovery patterns with metabolomics and transcriptomics.

Characterization and toxicity of nanoscale fragments in wastewater treatment plant effluent.

Much attention has been paid to extracting and isolating specific and well-known nanoparticles (especially for engineered nanomaterials) from complex environmental matrices. However, such research may not provide global information on actual contamination because nanoscale fragments exist as mixtures of various elements and matrices in the real environment. The present work first isolated and characterized nanoscale fragments in effluents from municipal wastewater treatment plants (WWTPs). The nanoscale fragments were found to be composed of 70-85% carbon and low amounts of oxygen, heavy metals and other elements and exhibited nanosheet topographies (approximately 0.87-1.31 nm thickness and 68-187 nm lateral length). Because the isolated nanoscale fragments were mixtures rather than one specific type of nanoparticle, they were present at high concentrations ranging from 0.07 to 0.55 mg/L. It was also found that the accumulation of nanoscale fragments in rice reached 0.59 mg/g under exposure to environmentally relevant concentrations, leading to marked phytotoxicity (e.g., ultrastructural damage to chloroplasts and mitochondria). Metabolic analysis revealed the toxicological mechanisms to be related to disorders of carbohydrate, amino acid and fatty acid metabolism. This study is the first to characterize the properties and analyze the toxicity of nanoscale fragments in the effluents of WWTPs. Given that WWTP effluents containing nanoscale fragments are continuously discharged to the soil, surface water and seas, nanoscale fragment materials deserve considerable attention in future work compared with the few widely studied engineered nanoparticles.

Aqueously Released Graphene Oxide Embedded in Epoxy Resin Exhibits Different Characteristics and Phytotoxicity of Chlorella vulgaris from the Pristine Form.

The environmental release of nanoparticles is attracting increasing attention. Graphene oxide (GO) embedded in epoxy resin (ER) is a popular composite that has been used in various fields, but the environmental release of GO-ER composites and the effects on organisms in the environment remain unknown. The present work found that GO-ER composites in water for 2-7 days resulted in the release of 0.3-2.1% GO-ER at nanoscale (2-3 nm thickness and approximately 70-130 nm lateral length). Interestingly, pristine GO quenched 30-45% hydroxyl and 12% nitroxide free radicals, whereas this capacity was not observed for the released particles from GO-ER. At environmentally relevant concentrations (µg/L), released GO-ER particles, but not GO or ER matrix, promoted algal reproduction by 34% and chlorophyll biosynthesis by 65-127% at 96 h. Released GO-ER entered algal cells and induced a slight increase in reactive oxygen species but did not elicit notable cell structure damage. The upregulated amino acids and phenylalanine metabolism, and the downregulated fatty acid biosynthesis contributed to algal growth promoted by released GO-ER. Previous studies of pristine nanoparticles were unable to reflect the environmental effects of released nanoparticles into the environment, and our research on the exposure-toxicological continuum adds important contributions to this field.

Strategies and knowledge gaps for improving nanomaterial biocompatibility.

With rapid development of nanotechnology and nanomaterials, nanosafety has attracted wide attention in all fields related to nanotechnology. As well known, a grand challenge in nanomaterial applications is their biocompatibility. It is urgent to explore effective strategies to control the unintentional effects. Although many novel methods for the synthesis of biocompatible and biodegradable nanomaterials are reported, the control strategy of nanotoxicity remains in its infancy. It is urgent to review the archived strategies for improving nanomaterial biocompatibility to clarify what we have done and where we should be. In this review, the achievements and challenges in nanomaterial structure/surface modifications and size/shape controls were analyzed. Moreover, the chemical and biological strategies to make nanomaterial more biocompatible and biodegradable were compared. Finally, the concerns that have not been studied well were prospected, involving unintended releases, life-cycle, occupational exposure and methodology.