High biological N fixation potential dominated by heterotrophic diazotrophs in alpine permafrost rivers on the Qinghai‒Tibet Plateau.

Biological nitrogen (N) fixation is a pivotal N source in N-deficient ecosystems. The Qinghai‒Tibet Plateau (QTP) region, which is assumed to be N limited and suboxic, is an ideal habitat for diazotrophs. However, the diazotrophic communities and associated N fixation rates in these high-altitude alpine permafrost QTP rivers remain largely unknown. Herein, we examined diazotrophic communities in the sediment and biofilm of QTP rivers via the nitrogenase (nifH) gene sequencing and assessed their N fixing activities via a 15N isotope incubation assay. Strikingly, anaerobic heterotrophic diazotrophs, such as sulfate- and iron-reducing bacteria, had emerged as dominant N fixers. Remarkably, the nifH gene abundance and N fixation rates increased with altitude, and the average nifH gene abundance (2.57 ± 2.60 × 108 copies g-1) and N fixation rate (2.29 ± 3.36 nmol N g-1d-1) surpassed that documented in most aquatic environments (nifH gene abundance: 1.31 × 105 ∼ 2.57 × 108 copies g-1, nitrogen fixation rates: 2.34 × 10-4 ∼ 4.11 nmol N g-1d-1). Such distinctive heterotrophic diazotrophic communities and high N fixation potential in QTP rivers were associated with low-nitrogen, abundant organic carbon and unique C:N:P stoichiometries. Additionally, the significant presence of psychrophilic bacteria within the diazotrophic communities, along with the enhanced stability and complexity of the diazotrophic networks at higher altitudes, clearly demonstrate the adaptability of diazotrophic communities to extreme cold and high-altitude conditions in QTP rivers. We further determined that altitude, coupled with organic carbon and phosphorus, was the predominant driver shaping diazotrophic communities and their N-fixing activities. Overall, our study reveals high N fixation potential in N-deficient QTP rivers, which provides novel insights into nitrogen dynamics in alpine permafrost rivers.

S-containing molecular markers of dissolved organic carbon attributing to riverine dissolved methane production across different land uses.

The emission of methane (CH4) from streams and rivers contributes significantly to its global inventory. The production of CH4 is traditionally considered as a strictly anaerobic process. Recent investigations observed a "CH4 paradox" in oxic waters, suggesting the occurrence of oxic methane production (OMP). Human activities promoted dissolved organic carbon (DOC) in streams and rivers, providing significant substrates for CH4 production. However, the underlying DOC molecular markers of CH4 production in river systems are not well known. The identification of these markers will help to reveal the mechanism of methanogenesis. Here, Fourier transform ion cyclotron mass spectrometry and other high-quality DOC characterization, ecosystem metabolism, and in-situ net CH4 production rate were employed to investigate molecular markers attributing to riverine dissolved CH4 production across different land uses. We show that endogenous CH4 production supports CH4 oversaturation and positively correlates with DOC concentrations and gross primary production. Furthermore, sulfur (S)-containing molecules, particularly S-aliphatics and S-peptides, and fatty acid-like compounds (e.g., acetate homologs) are characterized as markers of water-column aerobic and anaerobic CH4 production. Watershed characterization, including riverine discharge, allochthonous DOC input, turnover, as well as autochthonous DOC, affects the CH4 production. Our study helps to understand riverine aerobic or anaerobic CH4 production relating to DOC molecular characteristics across different land uses.

Legacy and alternative perfluoroalkyl acids in the Yellow River on the Qinghai-Tibet Plateau: Levels, spatiotemporal characteristics, and multimedia transport processes.

The source region of the Yellow River (SRYR) located in the northeast of the Qinghai-Tibetan Plateau is not only the largest runoff-producing area in the Yellow River Basin, but also the most important freshwater-supply ecological function area in China. In this study, the short-term spatiotemporal distribution of selected legacy and alternative perfluoroalkyl acids (PFAAs) in the SRYR was first investigated in multiple environmental media. Total PFAA concentrations were in the range of 1.16-14.3 ng/L, 4.25-42.1 pg/L, and 0.21-13.0 pg/g dw in rainwater, surface water, and sediment, respectively. C4-C7 PFAAs were predominant in various environmental matrices. Spatiotemporal characteristics were observed in the concentrations and composition profiles. Particularly, the spatial distribution of rainwater and the temporal distribution of surface water exhibited highly significant differences (p<0.01). Indian monsoon, westerly air masses, and local mountain-valley breeze were the driving factors that contributed to the change of rainwater. Rainwater, meltwater runoff, and precursor degradation were important sources of PFAA pollution in surface water. Organic carbon content was a major factor influencing PFAA distribution in sediment. These results provide a theoretical basis for revealing the regional transport and fate of PFAAs, and are also important prerequisites for effectively protecting the freshwater resource and aquatic environment of the Qinghai-Tibetan Plateau.

Effects of microplastics on sedimentary greenhouse gas emissions and underlying microbiome-mediated mechanisms: A comparison of sediments from distinct altitudes.

Microplastics (MPs) are emerging contaminants in aquatic ecosystems that can profoundly affect carbon and nitrogen cycling. However, the impact mechanisms of MPs on sedimentary greenhouse gas (GHG) emissions at distinct altitudes remain poorly elucidated. Here, we investigated the effects of polyvinyl chloride (PVC) and polylactic acid (PLA) on sedimentary CO2, CH4, and N2O emissions at distinct altitudes of the Yellow River. PVC increased the relative abundance of denitrifiers (e.g., Xanthobacteriaceae, Rhodocyclaceae) to promote N2O emissions, whereas PLA reduced the abundance of AOA gene and denitrifiers (e.g., Pseudomonadaceae, Sphingomonadaceae), impeding N2O emissions. Both PVC and PLA stimulated the growth of microbes (Saprospiraceae, Aquabacterium, and Desulfuromonadia) associated with complex organics degradation, leading to increased CO2 emissions. Notably, the concurrent inhibition of PLA on mcrA and pmoA genes led to its minimal impact on CH4 emissions. High-altitude MQ sediments, characterized by abundant substrate and a higher abundance of functional genes (AOA, AOB, nirK, mcrA), demonstrated higher GHG emissions. Conversely, lower microbial diversity rendered the low-altitude LJ microbial community more susceptible to PVC, leading to a more significant promotion on GHG emissions. This study unequivocally confirms that MPs exacerbate GHG emissions via microbiome-mediated mechanisms, providing a robust theoretical foundation for microplastic control to mitigate global warming.

Unraveling the Pollution and Discharge of Aminophenyl Sulfone Compounds, Sulfonamide Antibiotics, and Their Acetylation Products in Municipal Wastewater Treatment Plants.

Aminophenyl sulfone compounds (ASCs) are widely used in various fields, such as the pharmaceutical and textile industries. ASCs and their primary acetylation products are inevitably discharged into the environment. However, the high toxicity of ASCs could be released from the deacetylation of acetylation products. Still, the occurrence and ecological risks of ASCs and their acetylation products remain largely unknown. Here, we integrated all of the existing ASCs based on the core structure, together with their potential acetylation products, to establish a database covering 1105 compounds. By combining the database with R programming, 45 ASCs, sulfonamides, and their acetylation products were identified in the influent and effluent of 19 municipal wastewater treatment plants in 4 cities of China. 13 of them were detected for the first time in the aquatic environment, and 12 acetylation products were newly identified. The cumulative concentrations of 45 compounds in the influent and effluent were in the range of 231-9.96 × 103 and 26-2.70 × 103 ng/L, respectively. The proportion of the unrecognized compounds accounted for 60.6% of the influent and 62.8% of the effluent. Furthermore, nearly half of the ASCs (46.7%), other sulfonamides (49.9%), and their acetylation products (46.2%) were discharged from the effluent, posing a low-to-medium risk to aquatic organisms. The results provide a guideline for future monitoring programs, particularly for sulfadiazine and dronedarone, and emphasize that the ecological risk of ASCs, sulfonamides, and their acetylation products needs to be considered in the aquatic environment.

Biogeography and impact of nitrous oxide reducers in rivers across a broad environmental gradient on emission rates.

Microbial communities that reduce nitrous oxide (N2O) are divided into two clades, nosZI and nosZII. These clades significantly differ in their ecological niches and their implications for N2O emissions in terrestrial environments. However, our understanding of N2O reducers in aquatic systems is currently limited. This study investigated the relative abundance and diversity of nosZI- and nosZII-type N2O reducers in rivers and their impact on N2O emissions. Our findings revealed that stream sediments possess a high capacity for N2O reduction, surpassing N2O production under high N2O/NO3- ratio conditions. This study, along with others in freshwater systems, demonstrated that nosZI marginally dominates more often in rivers. While microbes containing either nosZI and nosZII were crucial in reducing N2O emissions, the net contribution of nosZII-containing microbes was more significant. This can be attributed to the nir gene co-occurring more frequently with the nosZI gene than with the nosZII gene. The diversity within each clade also played a role, with nosZII species being more likely to function as N2O sinks in streams with higher N2O concentrations. Overall, our findings provide a foundation for a better understanding of the biogeography of stream N2O reducers and their effects on N2O emissions.

Layer-specific mechanisms of perfluoroalkyl acid (PFAA) transport and partition in estuarine environments: Unveiling the depth-dependent differences.

Understanding of characteristics and transport of perfluoroalkyl acids (PFAAs) in heterogeneous estuarine environments is limited. Furthermore, the role of suspended particles (SPS) in different layers remains unclear. This study explores the multiphase distribution process and mechanism of PFAAs controlled by SPS across surface and bottom layers in five small estuaries. Peaks in PFAA concentrations are consistently observed at strongly stratified sites. Concentrations of the PFAAs in both surface and bottom SPS decreased as the degree of mixing increased from strongly stratified levels to well-mixed levels. The water-SPS partitioning of some short-chain PFAAs (PFBS, PFHxA, and PFHpA) is influenced by environmental factors (pH, depth, temperature, and salinity) due to electrostatic interactions, while the sorption of some long-chain PFAAs (PFOA, PFOS, and PFNA) is controlled by SPS and dissolved organic carbon (OC), driven by hydrophobic interactions. Additionally, SPS dominates OC transport in estuarine systems, except in sandy sediment environments. SPS plays a dominant role in PFAA partitioning in both surface and bottom water-SPS systems (p < 0.05), and salinity only significantly affects PFBS in bottom layer (p < 0.01). These findings are critical for understanding the drivers of PFAA partitioning and the roles of SPS in different layers, underscoring the necessity of considering particle-associated PFAA fractions in future coastal environmental management.

Photoaging of biodegradable nanoplastics regulates their toxicity to aquatic insects (Chironomus kiinensis) by impairing gut and disrupting intestinal microbiota.

Biodegradable plastic, a widely used ecofriendly alternative to conventional plastic, easily form nanoplastics (NPs) upon environmental weathering. However, the effects and underlying mechanisms governing the toxicity of photoaged biodegradable NPs to aquatic insects are not understood. In this study, we investigated the photoaging of polylactic acid nanoplastics (PLA-NPs, a typical biodegradable plastic) that were placed under xenon arc lamp for 50 days and 100 days and compared the toxicity of virgin and photoaged PLA-NPs to Chironomus kiinensis (a dominant aquatic insect). The results showed that photoaged PLA-NPs significantly decreased the body weight, body length and emergence rate of C. kiinensis. Additionally, photoaged PLA-NPs induced more severe gut oxidative stress, histological damage, and inflammatory responses than virgin PLA-NPs. Furthermore, the alpha diversity of gut microbiota was lower in photoaged PLA-NPs group than virgin PLA-NPs. The relative abundance of key gut bacteria related to intestinal barrier defense, immunity, and nutrient absorption was reduced more significantly in photoaged PLA-NPs group than virgin PLA, indirectly leading to stronger gut damage and growth reduction. A stronger impact of photoaged PLA-NPs on the gut and its microbiota occurred because photoaging reduced the size of NPs from 255.5 nm (virgin PLA) to 217.1 nm (PLA-50) and 182.5 nm (PLA-100), induced surface oxidation and enhancement of oxidative potential, and improved the stability of NPs, thereby exacerbating toxicity on the gut and its microbiota. This study provides insights into the effects of biodegradable NPs on aquatic insects and highlights the importance of considering biodegradable nanoplastic aging in risk assessments.

A wide survey of heavy metals-induced in-vitro DNA replication stress characterized by rate-limited replication.

Heavy metals (HMs) are environmental pollutants that pose a threat to human health and have been accepted to cause various diseases, including cancer and developmental disorders. DNA replication stress has been identified to be associated with such diseases. However, the effect of HMs exclusively on DNA replication stress is still not well understood. In this study, DNA replication stress induced by thirteen HMs was assessed using a simplified in-vitro DNA replication model. Two parameters, Cte/Ctc reflecting the cycle threshold value alteration and Ke/Kc reflecting the linear phase slope change, were calculated based on the DNA replication amplification curve to evaluate the rate of exponential and linear phases. These parameters were used to detect the replication rate reflecting in-vitro DNA replication stress induced by tested HMs. According to the effective concentrations and rate-limiting degree, HMs were ranked as follows: Hg, Ce > Pb > Zn > Cr > Cd > Co > Fe > Mn, Cu, Bi, Sr, Ni. Additionally, EDTA could relieve the DNA replication stress induced by some HMs. In conclusion, this study highlights the potential danger of HMs themselves on DNA replication and provides new insight into the possible links between HMs and DNA replication-related diseases.

Characterization and quantification of silver complexes with dissolved organic matter by size exclusion chromatography coupled to ICP-MS.

The fate and behavior of silver in aquatic systems is intricately determined by its interactions with dissolved organic matter (DOM). In this study, we have introduced a method for identification and quantification of silver-DOM complexes using size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). Our findings revealed that silver(I) was weakly bound to Suwannee River humic acid, fulvic acid, and natural organic matter (SRHA, SRFA, and SRNOM) in various media, resulting in facile dissociation during chromatographic separation. Suitable chromatographic conditions were determined for the elution of Ag-DOM complexes, involving the use of 0.5 mM ammonium acetate (pH 7) as the mobile phase and silver-aged column (pre-absorbing 0.1-0.7 µg silver(I)). SEC-UV and SEC-ICP-MS chromatograms revealed that Ag-binding fractions of DOM were dominated by its aromatic compounds. The quantification of silver-DOM complexes was achieved by SEC-ICP-MS combination with on-line isotope dilution. Silver at concentrations below 20 µg L-1 was mainly present in the form of organic complexes in low salinity water. These measurements aligned well with the results obtained using the equilibrium dialysis method. Species analyses of Ag-DOM complexes provide a deeper understanding of the reactivity, transport, and fate of silver in aquatic environments. ENVIRONMENTAL IMPLICATION: Ionic silver is highly toxic to aquatic organisms such as fish and zooplankton. The complexation of silver with binding sites within DOM significantly influences its speciation, mobility, and toxicity. Despite the complex and unknown structure of silver-DOM complexes, this study provided a SEC-ICP-MS method to identify and quantify these complexes in a range of media. By uncovering the formation of silver-DOM complexes across diverse media, this work enhances the comprehension of silver transformation processes and associated environmental risks in aquatic environments.

Nanoplastics Affect the Bioaccumulation and Gut Toxicity of Emerging Perfluoroalkyl Acid Alternatives to Aquatic Insects (Chironomus kiinensis): Importance of Plastic Surface Charge.

Persistent organic pollutants (POPs) have been widely suggested as contributors to the aquatic insect biomass decline, and their bioavailability is affected by engineered particles. However, the toxicity effects of emerging ionizable POPs mediated by differentially charged engineered nanoparticles on aquatic insects are unknown. In this study, 6:2 chlorinated polyfluoroalkyl ether sulfonate (F-53B, an emerging perfluoroalkyl acid alternative) was selected as a model emerging ionizable POP; the effect of differentially charged nanoplastics (NPs, 50 nm, 0.5 g/kg) on F-53B bioaccumulation and gut toxicity to Chironomus kiinensis were investigated through histopathology, biochemical index, and gut microbiota analysis. The results showed that when the dissolved concentration of F-53B remained constant, the presence of NPs enhanced the adverse effects on larval growth, emergence, gut oxidative stress and inflammation induced by F-53B, and the enhancement caused by positively charged NP-associated F-53B was stronger than that caused by the negatively charged one. This was mainly because positively charged NPs, due to their greater adsorption capacity and higher bioavailable fraction of associated F-53B, increased the bioaccumulation of F-53B in larvae more significantly than negatively charged NPs. In addition, positively charged NPs interact more easily with gut biomembranes and microbes with a negative charge, further increasing the probability of F-53B interacting with gut biomembranes and microbiota and thereby aggravating gut damage and key microbial dysbacteriosis related to gut health. These findings demonstrate that the surface charge of NPs can regulate the bioaccumulation and toxicity of ionizable POPs to aquatic insects.

Exposure levels and health implications of fungicides, neonicotinoid insecticides, triazine herbicides and their associated metabolites in pregnant women and men.

Exposure to pesticides can pose a series of advance effects on human health. However, the exposure levels and health implications of the current use pesticides and their metabolites in both men and pregnant women remain unclear. In this study, an analytical method was developed to quantify fungicides, neonicotinoid insecticides, triazine herbicides, and their metabolites in the human serum. Fifty of the 73 target pesticides and metabolites were detected in the human serum of men and pregnant women from Wuxi, China, which included 11 triazine herbicides and metabolites, 17 neonicotinoid insecticides and metabolites, and 22 fungicides. Fungicides had the highest cumulative concentration (49.5 ng/mL), followed by neonicotinoid insecticides and metabolites (6.38 ng/mL), and triazine herbicides and metabolites (5.10 ng/mL). Moreover, the estimated daily intake (EDI) of fungicides was 10.4 and 12.7 times higher than that of triazine herbicides (included their metabolites) and neonicotinoid insecticides (included their metabolites), respectively. Of the three categories of pesticides, exposure to fungicides contributed to the highest exposure risk within the hazard quotient in the range of 5.1 × 10-3-0.17. Correlation analysis revealed that the pesticide exposure levels in human serum were correlated with their maximum residue levels in vegetables and fruits. Pesticide exposure has also been correlated with the weight and Body Mass Index (BMI) of humans based on structural equation modeling. This study provides new insights into the exposure of men and pregnant women to a cocktail of fungicides, neonicotinoid insecticides, triazine herbicides and their metabolites.

Insights into adsorption behavior and mechanism of Cu(II) onto biodegradable and conventional microplastics: Effect of aging process and environmental factors.

The widespread promotion attempt of biodegradable plastics is considered as an effective solution to address conventional plastic pollution. However, the interaction of microplastics (MPs) easily broken down from biodegradable plastics with the coexisting pollutants in aquatic environments has gained less attention. Herein, we investigated the effects of the aging process and environmental factors on copper (Cu(II)) adsorption behavior by biodegradable polylactic acid and conventional polystyrene MPs. Results demonstrated that the aging process significantly altered physicochemical properties of both types of MPs, and PLA showed less resistance to aging. The aged polylactic acid MPs (aged-PLA) exhibited the far highest Cu(II) maximum adsorption capacity (7.13 mg/g) mainly due to its abundant oxygen-containing functional groups (OCFGs), followed by pristine polylactic acid (PLA, 6.08 mg/g), aged polystyrene (aged-PS, 0.489 mg/g) and pristine polystyrene (PS, 0.365 mg/g). The adsorption kinetics of Cu(II) on PLA MPs were controlled by film and intraparticle diffusion, while film diffusion governed the Cu(II) adsorption onto PS MPs. In addition to roles of rougher surface structure, greater surface area and pore filling, the complexation of OCFGs and electrostatic interaction were critical to the adsorption mechanism of aged-PLA and aged-PS, and cation-π interaction was associated with adsorption of aged-PS. Moreover, the adsorption capacity of Cu(II) on aged MPs gradually grew with the increasing pH from 4 to 7. Besides, humic acid significantly promoted the adsorption of Cu(II) at a low concentration (0-20 mg/L) due to the formation of binary mixtures of MPs-HA but inhibited the adsorption at a high concentration (50 mg/L) because of its competitive effect, suggesting the dual roles of humic acid in the adsorption process. Overall, our findings provide a better understanding of the adsorption behavior of metals on biodegradable MPs and emphasize their non-negligible risk as carriers of contaminant.

Bioconcentration of polycyclic aromatic hydrocarbons in different tissues of zebrafish (Danio rerio) investigated with PBTK model.

Due to the lipophilicity, polycyclic aromatic hydrocarbons (PAHs) are easily accumulated in fish. However, the research on PAH bioaccumulation process in different fish tissues and the relevant effect mechanisms are still deficient. The bioconcentration of PAHs (phenanthrene, anthracene, fluoranthene, and pyrene) in different zebrafish tissues (skin, fish muscle, gill, digestive tract, liver, gonad, and residual) was studied. It was found that there was a difference in the PAH concentrations in different zebrafish tissues. Compared with other tissues, the PAH concentration was highest in the skin and lowest in the fish muscle. For example, the steady-state concentration of phenanthrene in the skin was nearly five times higher than that in the muscle. PAH distribution was related with the lipid contents in different zebrafish tissues; however, the correlation was not significant (p > 0.05), indicating that the lipid content was not the determining factor for the PAH distribution. The distribution was also affected by the bioconcentration kinetics of PAHs in different zebrafish tissues, and the PAH hydrophobic properties. In addition, the physiological based toxicokinetic (PBTK) model showed good performance in predicting PAH internal concentrations, and it may be used to predict the concentrations of PAHs in different fish tissues in future.

Identification and Coexposure of Neonicotinoid Insecticides and Their Transformation Products in Retail Cowpea (Vigna unguiculata).

There is growing evidence that the transformation products of emerging contaminants in foodstuffs may pose a health risk to humans. However, the exact identities, levels, and estimated dietary intake (EDI) of neonicotinoid transformation products in crops remain poorly understood. We established an extended suspect screening strategy to investigate neonicotinoid insecticides and their transformation products in retail cowpea from 11 cities in Hainan Province, China. Forty-nine transformation products were identified in retail cowpea, of which 22-36 were found in 98.6% of the samples. Notably, 31 new transformation products were derived from new processes or a combination of different transformation processes. The mean concentrations of neonicotinoids and nine of the transformation products (with authentic standards) were in the ranges of 0.0824-5.34 and 0.0636-1.50 ng/g, respectively. The cumulative EDIs of the quantified transformation products were lower than those of parent neonicotinoids with the exception of clothianidin desmethyl, which had a ratio of 1157%. However, the coexistence of the other 40 transformation products (without authentic standards) in cowpea suggested that the exposure risk from all of the transformation products might be higher. This study demonstrated that pesticide transformation products should be considered in food chain risk assessments and included in future regulatory management.

Nitrous Oxide (N2O) Emissions Decrease Significantly under Stronger Light Irradiance in Riverine Water Columns with Suspended Particles.

Nitrous oxide (N2O) emissions from riverine water columns with suspended particles are important for the global N2O budget. Although sunlight is known to influence the activity of nitrogen-cycling microorganisms, its specific influence on N2O emissions in river systems remains unknown. This study analyzed the influences of light irradiance on N2O emissions in simulated oxic water columns with 15N-labeling and biological molecular techniques. Our results showed that N2O emissions were inhibited by light in the ammonium system (only 15NH4+ was added) and significantly decreased with increasing light irradiance in the nitrate system (only 15NO3- was added), despite contrasting variations in N2 emissions between these two systems. Lower N2O emission rates in the nitrate system under higher light conditions resulted from higher promotion levels of N2O reduction than N2O production. Increased N2O reduction was correlated to higher organic carbon bioavailability caused by photodegradation and greater potential for complete denitrification. Lower N2O production and higher N2O reduction were responsible for the lower N2O emissions observed in the ammonium system under light conditions. Our findings highlight the importance of sunlight in regulating N2O dynamics in riverine water columns, which should be considered in developing large-scale models for N2O processing and emissions in rivers.

Unexpected low CO2 emission from highly disturbed urban inland waters.

Constituents and functionality of urban inland waters are significantly perturbed by municipal sewage inputs and tailwater discharge from wastewater treatment plants. However, large knowledge gaps persist in understanding greenhouse gas dynamics in urban inland waters due to a lack of in situ measurements. Herein, via a 3-year field campaign (2018-2020), we report river and lake CO2 emission and related aquatic factors regulating the emission in the municipality of Beijing. Mean pCO2 (546 ± 481 µatm) in the two urban lakes was lower than global non-tropical freshwater lakes and CO2 flux in 47% of the lake observations was negative. Though average pCO2 in urban rivers (3124 ± 3846 µatm) was among the higher range of global rivers (1300-4300 µatm), average CO2 flux was much lower than the global river average (99.7 ± 147.5 versus 358.4 mmol m-2 d-1). The high pCO2 cannot release to the atmosphere due to the low gas exchange rate in urban rivers (average k600 of 1.3 ± 1.3 m d-1), resulting in low CO2 flux in urban rivers. Additionally, eutrophication promotes photosynthetic uptake and aquatic organic substrate production, leading to no clear relationships observed between pCO2 and phytoplankton photosynthesis or dissolved organic carbon. In consistence with the findings, CO2 emission accounted for only 32% of the total greenhouse gas (GHG) emission equivalence (CO2, CH4 and N2O) in Beijing waters, in contrast to a major role of anthropogenic CO2 to anthropogenic GHG in the atmosphere in terms of radiative forcing (66%). These results pointed to unique GHG emission profiles and the need for a special account of urban inland waters in terms of aquatic GHG emissions.

Differentially Charged Nanoplastics Induce Distinct Effects on the Growth and Gut of Benthic Insects (Chironomus kiinensis) via Charge-Specific Accumulation and Perturbation of the Gut Microbiota.

Nanoplastics (NPs), as an emerging contaminant, have usually been found charged in the environment, posing threats to aquatic animals. However, the underlying mechanisms governing the gut toxicity of differentially charged NPs to benthic insects are not well understood. In this study, the gut toxicity in larvae of Chironomus kiinensis exposed to negatively charged NPs (PS-COOH, 50 nm) and positively charged NPs (PS-NH2, 50 nm) at 0.1 and 1 g/kg was investigated through fluorescence imaging, histopathology, biochemical approaches, and 16S rRNA sequencing. The results showed that PS-NH2 caused more adverse effect on the larval growth performance and induced more severe oxidative stress, epithelial damage, and inflammatory responses in the gut than PS-COOH. The stronger impact caused by PS-NH2 was because the gut accumulated PS-NH2 more readily than PS-COOH for its negatively charged cell membrane. In addition, PS-NH2 were less agglomerated compared with PS-COOH, leading to an increased interaction with gut cell membranes and microbiota. Furthermore, alpha diversity and relative abundance of the keystone microbiota related to gut barrier and nutrient absorption were markedly lower exposed to PS-NH2 than PS-COOH, indirectly exacerbating stronger gut and growth damage. This study provides novel insights into the effect mechanisms underlying differentially charged NPs on benthic insects.

Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B12-Dependent Aromatic Reductive Dehalogenation.

Anaerobic bacteria transform aromatic halides through reductive dehalogenation. This dehalorespiration is catalyzed by the supernucleophilic coenzyme vitamin B12, cob(I)alamin, in reductive dehalogenases. So far, the underlying inner-sphere electron transfer (ET) mechanism has been discussed controversially. In the present study, all 36 chloro-, bromo-, and fluorobenzenes and full-size cobalamin are analyzed at the quantum chemical density functional theory level with respect to a wide range of theoretically possible inner-sphere ET mechanisms. The calculated reaction free energies within the framework of CoI···X (X = F, Cl, and Br) attack rule out most of the inner-sphere pathways. The only route with feasible energetics is a proton-coupled two-ET mechanism that involves a B12 side-chain tyrosine (modeled by phenol) as a proton donor. For 12 chlorobenzenes and 9 bromobenzenes with experimental data from Dehalococcoides mccartyi strain CBDB1, the newly proposed PC-TET mechanism successfully discriminates 16 of 17 active from 4 inactive substrates and correctly predicts the observed regiospecificity to 100%. Moreover, fluorobenzenes are predicted to be recalcitrant in agreement with experimental findings. Conceptually, based on the Bell-Evans-Polanyi principle, the computational approach provides novel mechanistic insights and may serve as a tool for predicting the energetic feasibility of reductive aromatic dehalogenation.

Promotion effect of ultraviolet light on graphene oxide aggregation in the presence of different climatic zone's humic and fulvic acid.

Aggregation of graphene oxide (GO) is significantly affected by dissolved organic matter (DOM) in natural waters, while DOM's climate zone and light irradiation is seldom considered. This study investigated the effect of humic/fulvic acid (HA/FA) from various climate zones of China on aggregation of small (200 nm) and large (500 nm) GO under 120-h UV irradiation. GO aggregation was promoted by HA/FA because UV irradiation decreased hydrophilicity of GO and steric forces among particles. GO generated electron and hole pair under UV irradiation, which reduce GO with more hydrophilic oxygen-containing functional group (C-O) to rGO with high hydrophobicity and oxidize DOM into organic matter with smaller molecular weight. Most severe GO aggregation was observed with Makou HA from Subtropical Monsoon climate zone and Maqin FA from Plateau and Mountain climate zone, which was primarily because HA/FA's high molecular weight and aromaticity dispersed GO initially that facilitated UV penetration. GO aggregation ratio was positively correlated with graphitic fraction content (R2 = 0.82-0.99) and negatively correlated with C-O group content (R2 = 0.61-0.98) in the presence of DOM under UV irradiation. This work highlights different dispersity of GO during photochemical reactions in various climate zones, providing new insight into the environmental implications of nanomaterial release.