Labile dissolved organic matter (DOM) and nitrogen inputs modified greenhouse gas dynamics: A source-to-estuary study of the Yangtze River.

Although rivers are increasingly recognized as essential sources of greenhouse gases (GHG) to the atmosphere, few systematic efforts have been made to reveal the drivers of spatiotemporal variations of dissolved GHG (dGHG) in large rivers under increasing anthropogenic stress and intensified hydrological cycling. Here, through a source-to-estuary survey of the Yangtze River in March (spring) and October (autumn) of 2018, we revealed that labile dissolved organic matter (DOM) and nitrogen inputs remarkably modified the spatiotemporal distribution of dGHG. The average partial pressure of CO2 (pCO2), CH4 and N2O concentrations of all sampling sites in the Yangtze River were 1015 ± 225 µatm, and 87.5± 36.5 nmol L-1, and 20.3 ± 6.6 nmol L-1, respectively, significantly lower than the global average. In terms of longitudinal and seasonal variations, higher GHG concentrations were observed in the middle-lower reach in spring. The dominant drivers of spatiotemporal variations in dGHG were labile, protein-like DOM components and nitrogen level. Compared with the historical data of dGHG from published literature, we found a significant increase in N2O concentrations in the Yangtze River during 2004-2018, and the increasing trend was consistent with the rising riverine nitrogen concentrations. Our study emphasized the critical roles of labile DOM and nitrogen inputs in driving the spatial hotspots, seasonal variations and annual trends of dGHG. These findings can contribute to constraining the global GHG budget estimations and controls of GHG emission in large rivers in response to global change.

Carbon and hydrogen isotopic evidence for atrazine degradation by electro-activated persulfate: Radical contributions and comparisons with heat-activated persulfate.

The activation ways of persulfate (PS) were dominate for pollutant degradation and energy consumption. For the first time, this research compared electro-activated PS and heat-activated PS from the perspective of isotope fractionation, in order to "fingerprinted" and precisely interpretate reaction contributions and degradation pathways. As results, PS can be electrochemically activated with atrazine (ATZ) removal rates of 84.8% and 88.8% at pH 4 and 7. The two-dimensional isotope plots (ɅC/H) values were 6.20 at pH 4 and 7.46 at pH 7, rather different from that of SO4·- -dominated process with ɅC/H value of -4.80 at pH 4 and -23.0 at pH 7, suggesting the weak contribution of SO4·-. ATZ degradation by electro-activated PS was controlled by direct electron transfer (DET) and ·OH radical, and ·OHPS (derived from PS activation) played the crucial role with contributing rate of 63.2%-69.1%, while DET and ·OHBDD (derived from electrolysis of H2O) contributed to 4.5-7.9% and 23.0%-30.8%, respectively. This was different from heat activation of PS, of which the latter was dominated by SO4·- with contributions of 83.9%-100%. The discrepant dominating reactive oxygen species should be responsible for their different degradation capabilities and pathways. This research provided isotopic interpretations for differences of PS activation mode, and further efforts can be made to realize the selective degradation by enhancing the specific reaction process.

Occurrence, mass loading, and post-control temporal trend of legacy perfluoroalkyl substances (PFASs) in the middle and lower Yangtze River.

Present study focused on per- and polyfluoroalkyl substances (PFASs) occurrence in dry and wet seasons in the middle and lower Yangtze River (YZR) and changing temporal trends after years of control. Results revealed that perfluorooctanoic acid (PFOA) was 75 % of total PFAS concentrations (∑11PFASs). ∑11PFASs were ranged 0.20-28.49 ng/L and 1.17-112.84 µg/kg in water and sediment. The logKoc of perfluoroalkyl carboxylic acids was positive with the carbon chain length (p < 0.05, r2 = 0.78). A meta-analysis of results from 16 peer-reviewed publications about PFASs in the YZR showed that fluorochemical industries strongly influenced the high PFAS levels in the detected scenes. PFOA was still the primary pollutant. Individual PFAS in the lower reach was higher than those in the middle reach. The mass loading of PFASs imported into the sea was 10.80 t/y. This study will help develop effective approaches for controlling emerging pollutants in the YZR.

Algal or bacterial community: Who can be an effective indicator of the impact of reclaimed water recharge in an urban river.

Reclaimed water has been widely utilized for water resource replenishment, yet little is known regarding its impacts on various microorganisms in the receiving water. To address this knowledge gap, we systematically investigated the responses of bacteria and algae to the recharge of reclaimed water by using the high-throughput sequencing technology in the urban Chaobai River. After the inputs of reclaimed water, lower contents of NO2--N, NH4+-N, and TP were observed in the downstream section compared to that of upstream without reclaimed water, indicating that reclaimed water could improve the water quality of the receiving water. Correspondingly, both bacterial and algal communities showed the decreased network complexity in the downstream section, but many common freshwater bacteria and typical bloom-forming algae were dominant in the downstream, potentially suggesting that algae were more sensitive to the local environmental conditions. More importantly, although nitrogen and phosphorus served as the paramount factors in shaping both bacterial and algal communities, environmental selection contributed more to algal rather than bacterial community, and simultaneously algal variations could further affect bacterial dynamics in the urban river. Overall, these findings revealed distinct characteristics of bacteria and algae in responding to the reclaimed water recharge, highlighting the superiority of algae in indicating environmental changes, especially in monitoring and regulating the replenishment of reclaimed water in urban rivers.

Distinct adaptive strategies and microbial interactions of soil viruses under different metal(loid) contaminations.

Viruses, as the most abundant organisms, significantly influence ecological function and microbial survival in soils, yet little was known about how viruses and virus-microbe interactions respond to environmental stresses induced by metal(loid) contaminations. Here, we conducted the metagenomic analysis to investigate the adaptative mechanisms of soil viruses under different metal(loid) contamination levels. By capturing a catalogue of 23,066 viruses, we found that viral communities exhibited the increased richness, diversity, and the temperate to lytic ratio in facing the highest metal(loid) contaminations. Meanwhile, viruses displayed obvious lineage-specific infection modes to distinct dominant hosts under different pollution levels. Viral functions linking to the inhibition of transcription and the enhancement of DNA repairment as well as multiple resistance not only contributed to coping with elevated multiple metal(loid) stresses, but also facilitated the adaptation and functioning of viral hosts. Moreover, the harmonious coexistence of viruses and resistant/pathogenic bacteria under the heaviest contaminations potentially exacerbated disseminating resistance and pathogenicity, while viruses under the lightest contaminations might be natural predators of resistant/pathogenic bacteria through lysing host cells. Overall, this study highlights the ecological importance of viral adaptation and the interactions between viruses and resistant/pathogenic bacteria in contaminated environments, contributing to developing virus-based approaches to soil restoration.

Roles of dissolved organic matter (DOM) in shaping the distribution pattern of heavy metal in the Yangtze River.

Dissolved organic matter (DOM) strongly influences the solid-liquid partitioning and migration characteristics of heavy metals, yet little is known about the metal distribution and risk with the participation of DOM in large riverine systems. This study investigated the spatiotemporal distribution of 14 heavy metals and DOM along the entire Yangtze River (over 6000 km), and highlighted the critical roles of DOM in regulating the environmental behaviors of heavy metals. Significant spatial variations of metal contents were observed, with the river source and lower reach remarkably different from the upper-middle reaches. Heavy metals in the Yangtze River were mainly from the natural sources with minor anthropogenic disturbance. We found DOM could promote the conversion of metals from solid to liquid phase and DOM with higher aromaticity showed higher metal affinities. Although low ecological risks were observed in the Yangtze River, potential risks of metal leaching warrant attention, especially for As, Cd and Sb in the middle-lower reaches with higher DOM content and aromaticity. This study established a source-to-sea investigative approach to evaluate the influences of DOM features on metal partitioning, which is crucial for the risk control and sustainable management of large rivers.

Virus-pathogen interactions improve water quality along the Middle Route of the South-to-North Water Diversion Canal.

Bacterial pathogens and viruses are the leading causes of global waterborne diseases. Here, we discovered an interesting natural paradigm of water "self-purification" through virus-pathogen interactions over a 1432 km continuum along the Middle Route of the South-to-North Water Diversion Canal (MR-SNWDC) in China, the largest water transfer project in the world. Due to the extremely low total phosphorus (TP) content (ND-0.02 mg/L) in the MR-SNWDC, the whole canal has experienced long-lasting phosphorus (P) limitation since its operation in 2015. Based on 4443 metagenome-assembled genomes (MAGs) and 40,261 nonredundant viral operational taxonomic units (vOTUs) derived from our recent monitoring campaign, we found that residential viruses experiencing extreme P constraints had to adopt special adaptive strategies by harboring smaller genomes to minimize nucleotide replication, DNA repair, and posttranslational modification costs. With the decreasing P supply downstream, bacterial pathogens showed repressed environmental fitness and growth potential, and a weakened capacity to maintain P acquisition, membrane formation, and ribonucleotide biosynthesis. Consequently, the unique viral predation effects under P limitation, characterized by enhanced viral lytic infections and an increased abundance of ribonucleotide reductase (RNR) genes linked to viral nuclear DNA replication cycles, led to unexpectedly lower health risks from waterborne bacterial pathogens in the downstream water-receiving areas. These findings highlighted the great potential of water self-purification associated with virus-pathogen dynamics for water-quality improvement and sustainable water resource management.

[Composition Structure and Influence Factors of Bacterial Communities in the Miyun Reservoir].

As the largest reservoir in North China, the Miyun Reservoir is the most important surface drinking water source in Beijing. Bacteria are key regulators of reservoir ecosystem structure and function, and exploring the community distribution characteristics of bacteria is important for maintaining water quality safety in reservoirs. The spatiotemporal distribution and environmental factors of bacterial communities in the water and sediment of the Miyun Reservoir were explored using the high-throughput sequencing method. The results showed a higher α-diversity and non-significant seasonal variation of the bacterial community in the sediment, and the abundant sedimental species were affiliated with Proteobacteria. For planktonic bacteria, Actinobacteriota was the dominant phylum, and the seasonal variance was represented by CL500-29_marine_group and hgcI_clade in the wet season and Cyanobium_PCC-6307 in the dry season. Additionally, obvious differences in key species were also found in water and sediment, and more indicator species were obtained in sedimental bacteria. Further, a more complex co-existence network was identified in water compared to that in sediment, indicating the strong ability of planktonic bacteria to resist environmental changes. Environmental factors had a significantly higher effect on the bacterial community of the water column than that of the sediment. Furthermore, SO2-4 and TN were the main factors affecting planktonic bacteria and sedimental bacteria, respectively. These findings revealed the distribution patterns and driving forces of the bacterial community in the Miyun Reservoir, which will provide important guidance for reservoir management and water-quality assurance.

Degradation pathways of atrazine by electrochemical oxidation at different current densities: Identifications from compound-specific isotope analysis and DFT calculation.

Current density was the key factor that impacted pollutant degradation by electrochemical oxidation, and reaction contributions at various current densities were non-negligible for the cost-effective treatments of organic pollutants. This research introduced compound specific isotope analysis (CSIA) into atrazine (ATZ) degradation by boron doped diamond (BDD) with current density of 2.5-20 mA/cm2, in order to provide "in-situ" and "fingerprint" analysis of reaction contributions with changed current densities. As results, the increased current density displayed a positive impact on ATZ removal. The ɅC/H values (correlations of Δδ13C and Δδ2H) were 24.58, 9.18 and 8.74 when current densities were 20, 4, and 2.5 mA/cm2, with ·OH contribution of 93.5%, 77.2% and 80.35%, respectively. While DET process favored lower current density with contribution rates up to ∼20%. What's more interesting, though the carbon and hydrogen isotope enrichment factors (εC and εH) were fluctuate, the ɅC/H linearly increased accompanied with applied current densities. Therefore, increasing current density was effective due to the larger ·OH contribution even though side reactions may occur. DFT calculations proved the increase of C-Cl bond length and the delocalization of Cl atom, confirming dechlorination reaction mainly occurred in the direct electron transfer process. While ·OH radical mainly attack the C-N bond on the side chain, which was more benefit to the fast decomposition of ATZ molecule and intermediates. It was forceful to discuss pollutant degradation mechanism by combining CSIA and DFT calculations. Target bond cleavage (i.e., dehalogenation reaction) can be conducted by changing reaction conditions like current density due to the significantly different isotope fractionation and bond cleavage.

Per- and polyfluoroalkyl substances (PFASs) in groundwater from a contaminated site in the North China Plain: Occurrence, source apportionment, and health risk assessment.

Per-and polyfluoroalkyl substances (PFASs) are manmade chemicals that have wide industrial and commercial application. However, little research has been carried out on PFASs pollution in groundwater from a previously contaminated site. Here, we investigated 43 PFASs in a monitoring campaign from two different aquifers in the North China Plain. Our results revealed that total PFASs concentrations (∑43PFASs) ranged from 0.22 to 3,776.76 ng/L, with no spatial or compositional differences. Moreover, perfluorooctanoic acid (PFOA) and perfluoroheptane sulfonate (PFHpS) were the dominant pollutants with mean concentrations of 177.33 ng/L and 51 ng/L, respectively. ∑43PFAS decreased with well depth due to the adsorption of PFASs to the aquifer materials. Water temperature, total organic carbon, dissolved oxygen, and total phosphorus concentrations were correlated to the PFAS concentrations. Principal component analysis indicated that the main sources of PFASs in groundwater were untreated industrial discharge, untreated domestic wastewater, food packaging, aqueous film forming foams and metal plating, and surface runoff, which overlapped with the industries that previously existed in a nearby city. Human health risks from drinking contaminated groundwater were low to the local residents, with children aged 1-2 years being the most sensitive group. One specific site with a high PFOA concentration was of concern, as it was several orders higher than the 70 ng/L recommended by US Environmental Protection Agency health advisory. This study provided baseline data for PFASs in a previously-contaminated site, which will help in the development of effective strategies for controlling PFASs pollution in the North China Plain.

Response of microbial nitrogen transformation processes to antibiotic stress in a drinking water reservoir.

Effects of antibiotics on microbial nitrogen transformation processes in natural aquatic ecosystems are largely unknown. In this study, we utilized the 15N stable isotope tracers and metagenomic sequencing to identify how antibiotics drive nitrogen transformation processes in Danjiangkou Reservoir, which is the largest artificial drinking water reservoir in China. We retrieved 51 nitrogen functional genes, and found that the highest abundances of nitrate reduction and denitrification-related genes occurred in dissimilatory nitrogen transformation pathways. 15N-labelling analysis substantiated that denitrification was the main pathway for nitrogen removal, accounting for 57.1% of nitrogen loss. Nitrogen functional genes and antibiotic resistance genes co-occurred in Danjiangkou Reservoir, and they were mainly carried by the denitrifying bacteria such as Rhodoferax, Polaromonas, Limnohabitans, Pararheinheimera, Desulfobulbus, and Pseudopelobacter. Genome annotation revealed that antibiotic deactivation, Resistance-Nodulation-Division and facilitator superfamily efflux pumps were responsible for the multiple-resistance to antibiotics in these bacteria. Moreover, antibiotics showed non-significant effects on nitrogen transformation processes. It is speculated that denitrifying bacteria harboring ARGs played crucial roles in protecting nitrogen transformation from low-level antibiotics stress in the reservoir. Our results highlight that denitrifying bacteria are important hosts of ARGs, which provides a novel perspective for evaluating the effects of antibiotics on nitrogen cycle in natural aquatic ecosystems.