Moderate increase of precipitation stimulates CO2 production by regulating soil organic carbon in a saltmarsh.

Saltmarsh is widely recognized as a blue carbon ecosystem with great carbon storage potential. Yet soil respiration with a major contributor of atmospheric CO2 can offset its carbon sink function. Up to date, mechanisms ruling CO2 emissions from saltmarsh soil remain unclear. In particular, the effect of precipitation on soil CO2 emissions is unclear in coastal wetlands, due the lack of outdoor data in real situations. We conducted a 7-year field manipulation experiment in a saltmarsh in the Yellow River Delta, China. Soil respiration in five treatments (-60%, -40%, +0%, +40%, and + 60% of precipitation) was measured in the field. Topsoils from the last 3 years (2019-2021) were analyzed for CO2 production potential by microcosm experiments. Furthermore, quality and quantity of soil organic carbon and microbial function were tested. Results show that only the moderate precipitation rise of +40% induced a 66.2% increase of CO2 production potential for the microcosm experiments, whereas other data showed a weak impact. Consistently, soil respiration was also found to be strongest at +40%. The CO2 production potential is positively correlated with soil organic carbon, including carbon quantity and quality. But microbial diversity did not show any positive response to precipitation sizes. r-/K-strategy seemed to be a plausible explanation for biological factors. Overall, our finding reveal that a moderate precipitation increase, not decrease or a robust increase, in a saltmarsh is likely to improve soil organic carbon quality and quantity, and bacterial oligotroph:copiotroph ratio, ultimately leading to an enhanced CO2 production.

Climate and mineral accretion as drivers of mineral-associated and particulate organic matter accumulation in tidal wetland soils.

Tidal wetlands sequester vast amounts of organic carbon (OC) and enhance soil accretion. The conservation and restoration of these ecosystems is becoming increasingly geared toward "blue" carbon sequestration while obtaining additional benefits, such as buffering sea-level rise and enhancing biodiversity. However, the assessments of blue carbon sequestration focus primarily on bulk SOC inventories and often neglect OC fractions and their drivers; this limits our understanding of the mechanisms controlling OC storage and opportunities to enhance blue carbon sinks. Here, we determined mineral-associated and particulate organic matter (MAOM and POM, respectively) in 99 surface soils and 40 soil cores collected from Chinese mangrove and saltmarsh habitats across a broad range of climates and accretion rates and showed how previously unrecognized mechanisms of climate and mineral accretion regulated MAOM and POM accumulation in tidal wetlands. MAOM concentrations (8.0 ± 5.7 g C kg-1 ) (±standard deviation) were significantly higher than POM concentrations (4.2 ± 5.7 g C kg-1 ) across the different soil depths and habitats. MAOM contributed over 51.6 ± 24.9% and 78.9 ± 19.0% to OC in mangrove and saltmarsh soils, respectively; both exhibited lower autochthonous contributions but higher contributions from terrestrial or marine sources than POM, which was derived primarily from autochthonous sources. Increased input of plant-derived organic matter along the increased temperature and precipitation gradients significantly enriched the POM concentrations. In contrast, the MAOM concentrations depended on climate, which controlled the mineral reactivity and mineral-OC interactions, and on regional sedimentary processes that could redistribute the reactive minerals. Mineral accretion diluted the POM concentrations and potentially enhanced the MAOM concentrations depending on mineral composition and whether the mineral accretion benefited plant productivity. Therefore, management strategies should comprehensively consider regional climate while regulating sediment supply and mineral abundance with engineering solutions to tap the OC sink potential of tidal wetlands.

Biomethane is produced by acetate cleavage, not direct interspecies electron transfer: genome-centric view and carbon isotope.

Understanding the source of methane (CH4) is of great significance for improving the anaerobic fermentation efficiency in bioengineering, and for mitigating the emission potential of natural ecosystems. Microbes involved in the process named direct interspecies electron transfer coupling with CO2 reduction, i.e., electrons released from electroactive bacteria to reduce CO2 into CH4, have attracted considerable attention for wastewater treatment in the past decade. However, how the synergistic effect of microbiota contributes to this anaerobic carbon metabolism accompanied by CH4 production still remains poorly understood, especial for wastewater with antibiotic exposure. Results show that enhancing lower-abundant acetoclastic methanogens and acetogenic bacteria, rather than electroactive bacteria, contributed to CH4 production, based on a metagenome-assembled genomes network analysis. Natural and artificial isotope tracing of CH4 further confirmed that CH4 mainly originated from acetoclastic methanogenesis. These findings reveal the contribution of direct acetate cleavage (acetoclastic methanogenesis) and provide insightsfor further regulation of methanogenic strategies.

Production of biochar from crop residues and its application for anaerobic digestion.

Anaerobic digestion (AD) is a viable and cost-effective method for converting organic waste into usable renewable energy. The efficiency of organic waste digestion, nonetheless, is limited due to inhibition and instability. Accordingly, biochar is an effective method for improving the efficiency of AD by adsorbing inhibitors, promoting biogas generation and methane concentration, maintaining process stability, colonizing microorganisms selectively, and mitigating the inhibition of volatile fatty acids and ammonia. This paper reviews the features of crop waste-derived biochar and its application in AD systems. Four critical roles of biochar in AD systems were identified: maintaining pH stability, promoting hydrolysis, enhancing the direct interspecies electron transfer pathway, and supporting microbial development. This work also highlights that the interaction between biochar dose, amount of organic component in the substrate, and inoculum-to-substrate ratio should be the focus of future research before deploying commercial applications.

Salt-tolerant plant moderates the effect of salinity on soil organic carbon mineralization in a subtropical tidal wetland.

Although salinization is widely known to affect cycling of soil carbon (C) in tidal freshwater wetlands, the role of the presence or absence of plants in mediating the responses of soil organic carbon (SOC) mineralization to salinization is poorly understood. In this study, we translocated soils collected from a tidal freshwater wetland to sites with varying salinities along a subtropical estuarine gradient and established unplanted and planted (with the salt-tolerant plant Cyperus malaccensis Lam.) mesocosms at each site. We simultaneously investigated cumulative soil CO2 emissions, C-acquiring enzyme activities, availability of labile organic C (LOC), and structures of bacterial and fungal communities. Overall, in the planted mesocosm, the soil LOC content and the activities of ß-1,4-glucosidase, cellobiohydrolase, phenol oxidase, and peroxidase increased with salinization. However, in the unplanted mesocosm, soil LOC content decreased with increasing salinity, whereas all the C-acquiring enzyme activities did not change. In addition, salinization favored the dominance of bacterial and fungal copiotrophs (e.g., γ-Proteobacteria, Bacteroidetes, Firmicutes, and Ascomycota) in the planted mesocosms. Contrarily, in the unplanted mesocosms salinization favored bacterial and fungal oligotrophs (e.g., α-Proteobacteria, Chloroflexi, Acidobacteria, and Basidiomycota). In both planted and unplanted mesocosms, cumulative soil CO2 emissions were affected by soil LOC content, activities of C-acquiring enzymes, and microbial C-use trophic strategies. Overall, cumulative soil CO2 emissions increased by 35% with increasing salinity in the planted mesocosm but decreased by 37% as salinity increased in the unplanted mesocosm. Our results demonstrate that the presence or absence of salt-tolerant plants can moderate the effect of salinity on SOC mineralization in tidal wetland soils. Future C prediction models should embed both planted and unplanted modules to accurately simulate cycling of soil C in tidal wetlands under sea level rise.

Rapid removal of chloramphenicol via the synergy of Geobacter and metal oxide nanoparticles.

The wide use of chloramphenicol and its residues in the environments are an increasing threat to human beings. Electroactive microorganisms were proven with the ability of biodegradation of chloramphenicol, but the removal rate and efficiency need to be improved. In this study, a model electricigens, Geobacter metallireducens, was supplied with and Fe3O4 and MnO2 nanoparticles. Five times higher chloramphenicol removal rate (0.71 d-1) and two times higher chloramphenicol removal efficiency (100%) was achieved. Fe3O4 and MnO2 nanoparticles highly increased the current density and NADH-quinone oxidoreductase expression. Fe3O4 nanoparticles enhanced the expression of alcohol dehydrogenase and c-type cytochrome, while MnO2 nanoparticles increased the transcription of pyruvate dehydrogenase and Type IV pili assembly genes. Chloramphenicol was reduced to a type of dichlorination reducing product named CPD3 which is a benzene ring containing compound. Collectively, Fe3O4 and MnO2 nanoparticles increased the chloramphenicol removal capacity in MFCs by enhancing electron transfer efficiency. This study provides new enhancing strategies for the bioremediation of chloramphenicol in the environments.

In situ electrochemical synthesis of graphene-poly(arginine) composite for p-nitrophenol monitoring.

Para-Nitrophenol (p-nitrophenol) is a common industrial pollutant occurring widely in water bodies, yet actual monitoring methods are limited. Herein we proposed a fully electrochemically in situ synthesized graphene-polyarginine composite functionalized screen printed electrode, as a novel p-nitrophenol sensing platform. The electrode was characterized by morphologic, spectrometric and electrochemical techniques. p-nitrophenol in both pure aqueous solution and real water samples was tested. Results show a detection limit as low as the nanomolar level, and display a linear response and high selectivity in the range of 0.5-1250 µM. Molecular simulation reveals a detailed synergy between graphene and poly-arginine. The preferable orientation of nitrophenol molecules on the graphene interface in the presence of poly-arginine induces H- and ionic binding. This sensor is an ideal prototype for p-nitrophenol quantification in real waters.

Alizarin-graphene nanocomposite for calibration-free and online pH monitoring of microbial fuel cell.

Microbial fuel cells (MFCs) are sensitive to acidity variations in both bioelectricity generation and biochemical digestion aspects, therefore online pH monitoring is of necessity to guarantee optimal function of MFCs. Present pH meters hardly fulfill this special need. In this work, we designed a novel voltammetric pH sensor based on electrochemically reduced graphene oxide (rGO) modified screen printed electrode. By surface doping of alizarin, good linearity of pH sensing over the range of 4.0-9.0 can be realized. Fast readout can be acquired within 15 s for each test. pH monitoring for artificial wastewater with inoculum of granular activated sludge in a MFC was successfully illustrated. Specially, it was verified that the performance was improved with alizarin doping due to the enhanced rGO surface proton diffusion. This approach provides an online, calibration-free and long stable pH monitoring method for the future MFC development.

Promotion of methane production by magnetite via increasing acetogenesis revealed by metagenome-assembled genomes.

Metal oxides are wildly studied to enhance anaerobic digestion and the methanogenic process, which is generally interpreted by increased direct interspecies electron transfer (DIET). Yet microbial mechanisms involved are under debate. Herein, methane production dynamics were analyzed, and acceleration on biogas accumulation was presented. Complementing previous findings, Fe3O4 nanoparticles stimulated bacterial fermentation rather than methanogenesis or syntropy between electro-microorganism and methanogen. More importantly, metagenome-assembled genomes proved that Fe3O4 nanoparticles increased acetogenesis by Parabacteroides chartae, which provided abundant substrates for acetoclastic methanogenesis. Interestingly, the weakly conductive V3O7·H2O nanowires increased potential hydrogen-producing bacteria, Brevundimonas, and electro-microorganisms, Clostridium and Rhodoferax, which is convenient for conducting DIET. Collectively, conductivity may not be a critical factor in mediating DIET and distinct strategies of metal oxides on methane production propose more possibilities, such as fermentation process.

Identifying the physicochemical properties of ß-cyclodextrin polymers that determine the adsorption of perfluoroalkyl acids.

Cyclodextrin polymers (CDPs) are emerging adsorbents with demonstrated potential to remove perfluoroalkyl acids (PFAAs) from water. However, little is known about how the physicochemical properties of different types of CDPs determine PFAA adsorption on CDPs. In this study, we investigated the adsorption performance of 34 CDPs which consist of 14 different crosslinkers and exhibit a wide range of physicochemical properties. The performance metrics included adsorption kinetics, equilibrium adsorption density, and adsorption affinity for six PFAAs. We then used complementary bivariate and multivariate analyses to discover relationships between sixteen measurable physicochemical properties of the CDPs and their performance as adsorbents. We found that: (1) CDPs with a less negative or more positive surface charge will exhibit enhanced adsorption of all types of PFAAs; (2) CDPs with greater porosity and surface area will exhibit enhanced adsorption kinetics for all types of PFAAs; (3) CDPs with greater crosslinker content will exhibit enhanced adsorption of short-chain PFAAs; (4) CDPs containing more hydrophobic crosslinkers will exhibit enhanced equilibrium adsorption density and adsorption affinity for longer-chain PFAAs; and (5) CDPs with smaller particle sizes will exhibit enhanced adsorption kinetics and equilibrium adsorption density for all PFAAs. These insights will enable the further development of CDPs and other novel adsorbents to optimize their performance for removing PFAAs during water and wastewater treatment or groundwater remediation.

Proteomics reveal biomethane production process induced by carbon nanotube.

Biomethane produced by methanogenic archaea is a main greenhouse resource of terrestrial and marine ecosystems, which strongly affects the global environment change. Conductive materials, especially nano-scale, show considerable intervention on biomethane production potential, but the mechanism is still unclear. Herein, we precisely quantified the absolute abundance of Methanosarcina spp. proteins affected by carbon nanotubes (CNTs) using tandem mass tag (TMT) proteomics technology. Among the 927 detectable proteins, more than three hundred, 304, showed differential expression. Gene Set Enrichment Analysis on KEGG pathways and GO biological processes revealed a trend of decreased protein synthesis induced by CNTs, suggesting these conductive nanomaterials may replace part of the cell structure and function. Interestingly, increased acetoclastic methanogenesis actually came at the expense of reduced protein synthesis in related pathways. CNTs stimulated biomethane production from acetate by stimulating intracellular redox activity and the -COOH oxidation process. These findings enhanced the understanding of the biomethane production process affected by conductive materials.

Augmentation of chloramphenicol degradation by Geobacter-based biocatalysis and electric field.

Electroactive microorganisms and electrochemical technologies have been separately used for environmental remediation such as antibiotics removal, yet the efficiency of coupling these two methods for chlorinated antibiotics removal is poorly known. Here we tested the synergy of Geobacter sulfurreducens PCA, an electroactive bacteria, and an electrical field, on chloramphenicol removal. Removal is increased two-fold by increasing the temperature from 30°C to 37°C. The cyclic voltammograms and chronoamperometry tests demonstrated that G. sulfurreducens PCA catalyzed chloramphenicol chemical reduction with electrode as excusive electron donor. A critical voltage, -0.6 to -0.5 V vs. Ag/AgCl, was discovered for chloramphenicol degradation with an increase of removal rate about 2.62-folds, from 31.06% to 81.41%. Combined removal with both G. sulfurreducens PCA and an electrical field increased the apparent rate constant and reached 82.77% removal at -0.5 V. Specially, the combined removal at -0.5 V even presented more robust removal efficiency compared to -0.6 V (78.64%) without G. sulfurreducens PCA. Mass spectrometry of degradation products indicates the reduction of nitro into amine groups, and dechlorination into less toxic compounds. Overall, combined biocatalysis and an electrical field is a promising method to remove antibiotics from polluted environments.

Insight into the Variability of the Nitrogen Isotope Composition of Vehicular NOx in China.

Nitrogen isotope (δ15N) monitoring is a potentially powerful tool in tracing atmospheric nitrogen oxides (NOx); however, the isotopic fingerprint of vehicle exhaust remains poorly interpreted. This deficiency limits our understanding of the origin of atmospheric haze pollution, especially in China. In this study, we systemically explored the δ15N-NOx fingerprints of various vehicle exhausts (n = 137) in China. The δ15N-NOx values of vehicle exhausts ranged from -18.8‰ to +6.4‰, presenting a significant correlation with NOx concentrations (p < 0.01). The highest δ15N-NOx values were observed for liquefied petroleum gas vehicles (-0.1 ± 1.8‰), followed by gasoline vehicles (-7.0 ± 4.8‰) and diesel vehicles (-12.7 ± 3.4‰), all of which displayed a rising trend as emissions standards were continuously updated. The δ15N-NOx values under working conditions followed the trend warm start (-5.9 ± 5.0‰) > driving (-7.3 ± 5.9‰) > cold start (-9.2 ± 2.7‰). By establishing a suitable model for assessing representative δ15N-NOx values, the δ15N-NOx values of various vehicles, including different fuel types with different emission standards, were evaluated. A model of δ15N-NOx associated with motor vehicle data was developed, which estimated the national δ15N-NOx value of vehicle emissions to be -12.6 ± 2.2‰, but there was considerable variation among different target areas in China.

Effect of Antibiotics on the Microbial Efficiency of Anaerobic Digestion of Wastewater: A Review.

Recycling waste into new materials and energy is becoming a major challenge in the context of the future circular economy, calling for advanced methods of waste treatment. For instance, microbially-mediated anaerobic digestion is widely used for conversion of sewage sludge into biomethane, fertilizers and other products, yet the efficiency of microbial digestion is limited by the occurrence of antibiotics in sludges, originating from drug consumption for human and animal health. Here we present antibiotic levels in Chinese wastewater, then we review the effects of antibiotics on hydrolysis, acidogenesis and methanogenesis, with focus on macrolides, tetracyclines, ß-lactams and antibiotic mixtures. We detail effects of antibiotics on fermentative bacteria and methanogenic archaea. Most results display adverse effects of antibiotics on anaerobic digestion, yet some antibiotics promote hydrolysis, acidogenesis and methanogenesis.

Inhibition effect of polyvinyl chloride on ferrihydrite reduction and electrochemical activities of Geobacter metallireducens.

Geobacter metallireducens GS15, a model of dissimilatory iron-reducing bacteria, is the key regulator in biogeochemical iron cycling. How the emerging contaminant microplastics involved in the iron cycling are driven by microbes on the microscale remains unknown. Hence, the influences of two typical microplastics, polybutylene terephthalate-hexane acid (PBAT) and polyvinyl chloride (PVC), were explored on the activity of G. metallireducens GS15 with ferrihydrite or ferric citrate as the respective electron acceptors. The results showed that the iron (II) contents in PBAT- and PVC-treatment groups were 16.79 and 6.81 mM, respectively, at the end of the experiment. Compared with the PBAT-treatment group, scanning electron microscopy and energy dispersive spectrometery revealed that merely a small amount of iron-containing products covered the surface of PVC. Moreover, PBAT and PVC could both retard the electroactivity of G. metallireducens GS15 at the beginning of microbial fuel cell operation. On the basis of the results above, microplastic PVC might exhibit potential inhibition of the iron cycling process driven by G. metallireducens GS15 with ferrihydrite as the terminal electron acceptor. This study extended our understanding of the influence of the microplastics PBAT and PVC on microbially mediated biogeochemical iron cycling. The findings might have an important implication on the biogeochemical elements cycling in the ecosystem with the involvement of emerging contaminant microplastics.

Methylobacter accounts for strong aerobic methane oxidation in the Yellow River Delta with characteristics of a methane sink during the dry season.

Recent investigations demonstrate that some coastal wetlands are atmospheric methane sinks, but the regulatory mechanisms are not clear. Here, the main pathway and operator of methane oxidation in the Yellow River Delta (YRD) wetland, a methane source in the wet season but a methane sink in the dry season, were investigated. The anaerobic oxidation of methane (AOM) and aerobic methane oxidation (AMO) abilities of wetland soil were measured, and the microbial community structure was analyzed. The experimental results showed that AMO was active throughout the year. In contrast, AOM was weak and even undetected. The microbial community analysis indicated that Methylomicrobium and Methylobacter potentially scavenged methane in oxic environments. A representative strain of Methylobacter, which was isolated from the soil, presented a strong AMO ability at high concentrations of methane and air. Overall, this study showed that active AMO performing by Methylobacter may account for methane sink in the YRD wetland during the dry season. Our research not only has determined the way in which methane sinks are formed but also identified the potential functional microbes. In particular, we confirmed the function of potential methanotroph by pure culture. Our research provides biological evidence for why some wetlands have methane sink characteristics, which may help to understand the global methane change mechanism.

Resorcinarene Cavitand Polymers for the Remediation of Halomethanes and 1,4-Dioxane.

Disinfection byproducts such as trihalomethanes are commonly found in drinking water. Trihalomethanes are formed upon chlorination of natural organic matter found in many drinking water sources. Inspired by molecular CHCl3⊂cavitand host-guest complexes, we designed porous polymers composed of resorcinarene receptors. These materials show higher affinity for halomethanes than a specialty activated carbon used for trihalomethane removal. The cavitand polymers show similar removal kinetics as activated carbon and have high capacity (49 mg g-1 of CHCl3). These materials maintain their performance in drinking water and can be thermally regenerated. Cavitand polymers also outperform commercial resins for 1,4-dioxane adsorption, which contaminates many water sources. These materials show promise for water treatment and demonstrate the value of using supramolecular receptors to design adsorbents for water purification.

Impacts of the rhizosphere effect and plant species on organic carbon mineralization rates and pathways, and bacterial community composition in a tidal marsh.

Despite the growing recognition regarding the carbon cycle in the rhizosphere of upland ecosystems, little is known regarding the rhizosphere effect on soil organic carbon (SOC) mineralization in tidal marsh soils. In the current study, in situ rhizobox experiments (including rhizosphere and inner and outer bulk soil) were conducted in an estuarine tidal marsh. Our results showed that a higher abundance of total bacteria, Geobacter, dsrA and mcrA and lower α-diversity were observed in the rhizosphere relative to the bulk soil. Rhizosphere effects shifted the partition of terminal metabolic pathways from sulfate reduction in the bulk soil to the co-dominance of microbial Fe(III) and sulfate reduction in the rhizosphere. Although the rhizosphere effect promoted the rates of three terminal metabolic pathways, it showed greater preference towards microbial Fe(III) reduction in the tidal marsh soils. Plant species had little impact on the partitioning of terminal metabolic pathways, but did affect the potential of total SOC mineralization together with the abundance and diversity of total bacteria. Both the rhizosphere effect and plant species influenced the bacterial community composition in the tidal marsh soils; however, plant species had a less pronounced impact on the bacterial community compared with that of the rhizosphere effect.

Reduction of a Tetrafluoroterephthalonitrile-ß-Cyclodextrin Polymer to Remove Anionic Micropollutants and Perfluorinated Alkyl Substances from Water.

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per- and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A ß-cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN-CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN-CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN-CDP to primary amines, which reverses its affinity towards charged MPs. TFN-CDP exhibits adsorption distribution coefficients (log KD values) of 2-3 for cationic MPs and -0.5-1.5 for anionic MPs, whereas the reduced TFN-CDP exhibits log KD values of -0.5-1.5 for cationic MPs and 2-4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80-98 % removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD-based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors.

Stimulation of ferrihydrite nanorods on fermentative hydrogen production by Clostridium pasteurianum.

Conversion of organic matter to biohydrogen possesses promising application potential. In this study, low-cost ferrihydrite nanorods were used to enhance hydrogen production by Clostridium pasteurianum. The maximum cumulative hydrogen production and the hydrogen yield were 1.03 mmol and 3.55 mol H2/mol glucose, respectively, which were 68.9% and 15.6% higher than those of the batch groups without ferrihydrite addition. Moreover, in comparison with magnetite and hematite nanoparticles, ferrihydrite presented the best stimulation for hydrogen evolution. The enhancement mechanisms were explored based on metabolic distribution, gene expression, enzymatic activity, and metabolite determination, such as Fe(II) concentration and pH value. The potential stimulation mechanisms are summarized as follows: ferrihydrite improves glucose conversion efficiency and promotes cell growth; ferrihydrite elevates the transcripts and activity of hydrogenase; and ferrihydrite reduction via its buffer function could ease acidification. This study demonstrates that ferrihydrite addition is an effective and green strategy to enhance fermentative hydrogen production.