Fen Sites Research Articles

Site-dependent carbon and greenhouse gas balances of five fen and bog soils after rewetting and establishment of Phalaris arundinacea paludiculture

Peatlands cover 3 % of the Danish land area, but drainage of these areas contributes to approximately 25 % of the total agricultural greenhouse gas (GHG) emissions. Paludiculture, defined as agriculture on wet or rewetted peatlands, has been proposed as a strategy to mitigate GHG emissions while keeping up production. However, little is known about the net GHG effects during establishment and how it is influenced by soil biogeochemical conditions. In this study, we determined annual carbon balances of five Danish peatlands, three fens and two bogs, for the first year of cultivation with reed canary grass (RCG) with two annual cuts in a mesocosm set-up under controlled conditions. Biomass yields were highly variable, ranging between 0.8 and 7.4 t dry matter (DM) ha−1 yr−1, and significantly higher on fen peat soils. Ecosystem respiration (Reco) fluxes of CO2 were naturally highest from sites with high biomass establishment. Methane emissions were site-specific, ranging between 0.03 and 1.85 t CH4 (CO2eq ha−1 yr−1), and affected by biomass growth, as well as bulk density and the iron content within soil. Nitrous oxide fluxes were negligible, despite nitrogen (N) fertilisation with 200 kg N ha−1 yr−1. Driven by net primary production (NPP) we found that the fen sites were GHG sinks, with a global warming potential (GWP) of −1.3 to −11.5 t CO2eq ha−1 yr−1 during the first year of rewetting and RCG establishment. The bogs remained sources of carbon (5.3 t CO2eq ha−1 yr−1). Our results highlighted that the nutrient-rich Danish fen peatlands showed a potential for GHG mitigation by paludiculture under extensive agricultural management, while this was not the case for the bog sites due to poor biomass establishment. In conclusion, we found the highest GHG mitigation potential by rewetting and RCG paludiculture on nutrient-rich fen peatlands.

Boosting OER activity of Fe-N Moieties via Ni induced d-Orbital Tailoring for durable rechargeable Zn-Air batteries

Fe-N-C-based catalysts are considered the most promising Pt candidates due to their high oxygen reduction reaction (ORR) activity and low cost, whereas their oxygen evolution reaction (OER) performance is extremely poor due to the sluggish O-O coupling process, which hampers the practical application of rechargeable zinc-air batteries. Here, we in situ infiltrate Ni and Fe ions into metal triazolidine (MET)-derived N-doped porous carbon via a microporous confinement-pyrolysis strategy to enhance the OER activity of the Fe-N sites. The introduction of Ni induced the electronic delocalization of Fe atoms at the Fe-N center, which lowered the adsorption energy barriers for the decisive velocity step (O*→OOH*), thus accelerating the O-O bond coupling and OER kinetics. In addition, the preferential formation of NiOOH at high OER potentials ensures the catalytic stability of zinc-air batteries by trapping Fe ions escaping from carbon corrosion to form FeOOH. The optimized catalyst (FeNi-NC) has an overpotential of only 351 mV at a current density of 50 mA cm−2 under alkaline conditions. More importantly, the assembled ZABs can be stably charged and discharged for more than 500 h at 10 mA cm−2, demonstrating excellent battery charging and discharging stability. This work shows the great potential of strong electronic interactions between polymetals to improve Fe-N-C catalysts.

Soil water repellency and its importance for the climate-smart sustainable management of fen peatland soils in Central Poland

The paper aims to assess potential soil water repellency (SWR) in the surface layers of long-term agricultural fen soils. Furthermore, we attempt to enhance our understanding of the links between selected soil properties (e.g., secondary transformation, total organic carbon (TOC) content) and SWR in differently used (grasslands and arable lands) fen soils in the temperate climate zone. The study was conducted in the Grójec Valley, Central Poland. The soil samples for laboratory analyses were collected in June 2022 from 64 sampling points – 56 grassland and 8 arable sites. We found that secondary soil transformation (mursh forming process) was significantly positively correlated with SWR – determined by MED (molarity of ethanol droplet) and WDPT (water drop penetration time) methods (r = 0.42 and r = 0.40, p < 0.05) only in the organic samples (i.e., mursh). The significant positive correlation between SWR and TOC content (r = 0.73 (MED) and r = 0.74 (WDPT), p < 0.05) indicates that, as well as organic matter depletion, there was a decrease in the water repellency of the studied soils. Our results indicate that study fen sites should be rewetted, and that the implementation of the paludiculture must take place in the near future. At a minimum, further arable cultivation of organic soils should be avoided, as they are the most vulnerable to secondary transformation and exhibit high SWR values. Furthermore, in the case of crop production on post-organic soils, it is recommended that the conservation tillage method is applied to prevent further depletion of soil organic matter content.

Nonmetal Doping Modulates Fe Single-Atom Catalysts for Enhancement in Peroxidase Mimicking via Symmetry Disruption, Distortion, and Charge Transfer.

Developing biomimetic catalysts with excellent peroxidase (POD)-like activity has been a long-standing goal for researchers. Doping nonmetallic atoms with different electronegativity to boost the POD-like activity of Fe-N-C single-atom catalysts (SACs) has been successfully realized. However, the introduction of heteroatoms to regulate the coordination environment of the central Fe atom and thus influence the activation of the H2O2 molecule in the POD-like reaction has not been extensively explored. Herein, the effect of different doping sites and numbers of heteroatoms (P, S, B, and N) on the adsorption and activation of H2O2 molecules of Fe-N sites is thoroughly investigated by density functional theory (DFT) calculations. In general, alternation in the catalytic efficiency directly depends on the transfer of electrons and the geometrical shifts near the Fe-N site. First, the symmetry disruption of the Fe-N4 site by P, S, and B doping is beneficial to the activation of H2O2 due to a significant reduction in the adsorption energies. In some cases, without Fe-N4 site disruption, the configurations fail to modulate the adsorption behavior of H2O2. Second, Fe-N-P/S configurations exhibit a stronger affinity for H2O2 molecules due to the significant out-of-plane distortions induced by larger atomic radii of P and S. Moreover, the synergistic effects of Fe and doping atoms P, S, and B with weaker electronegativity than that of N atoms promote electron donation to generated oxygen-containing intermediates, thus facilitating subsequent electron transfer with other substrates. This work demonstrates the critical role of tuning the coordinating environment of Fe-N active centers by heteroatom doping and provides theoretical guidance for controlling the types by breaking the symmetry of SACs to achieve optimal POD-like catalytic activity and selectivity.

Targeted activation of alcoholic sp3 Cα-H by H-bonding protection of O–H for the hydroxyalkylation of N-heterocycles

The direct sp3 C–H functionalization of alcohol with N-heterocycles is the most atom-economical pathway to produce hydroxyalkylated N-heterocycles. However, the targeted C–H activation to enable the direct C–C coupling still remains of great challenge due to the concomitant activation of alcoholic O–H. This work puts forward a H-bonding protection for alcoholic O–H for the targeted activation of alcoholic Cα-H bonds. Atomic Fe-N sites anchored in graphitic carbon nitride with uncoordinated nitrogen sites has thus been proposed for this strategy, in which atomic Fe(II)-N sites are supposed to be responsible for the targeted activation of alcoholic Cα-H and the surface uncoordinated nitrogen to for the H-bonding with alcoholic O–H. To demonstrate the strategy, the precise modulation on the atomic Fe-N coordination in the 6-fold cavity from three heptazines have been elaborated. Atomic Fe with four N atoms from two heptazines assisted with the uncoordinated N from the free one heptazine has presented a synergistic H-bonding protection of alcoholic O–H bonds. As a result, the targeted generation and excellent stabilization of hydroxyethyl radicals have been achieved under ambient temperature. The strategy has been successfully applied for 1-propanol, 2-propanol, 1-butanol, and 1-pentanol, thus achieving efficient C–C formation in the hydroxyalkylation of varied N-heterocycles.

Simultaneous elimination of antibiotic-resistant bacteria and antibiotic resistance genes by different Fe-N co-doped biochars activating peroxymonosulfate: The key role of pyridine-N and Fe-N sites

The coexistence of antibiotic resistance genes (ARGs) and antibiotic-resistant bacteria (ARB) in the environment poses a potential threat to public health. In our study, we have developed a novel advanced oxidation process for simultaneously removing ARGs and ARB by two types of iron and nitrogen-doped biochar derived from rice straw (FeN-RBC) and sludge (FeN-SBC). All viable ARB (approximately 108 CFU mL−1) was inactivated in the FeN-RBC/ peroxymonosulfate (PMS) system within 40 min and did not regrow after 48 h even in real water samples. Flow cytometry identified 96.7 % of dead cells in the FeN-RBC/PMS system, which verified the complete inactivation of ARB. Thorough disinfection of ARB was associated with the disruption of cell membranes and intracellular enzymes related to the antioxidant system. Whereas live bacteria (approximately 200 CFU mL−1) remained after FeN-SBC/PMS treatment. Intracellular and extracellular ARGs (tetA and tetB) were efficiently degraded in the FeN-RBC/PMS system. The production of active species, primarily •OH, SO4•- and Fe (IV), as well as electron transfer, were essential to the effective disinfection of FeN-RBC/PMS. In comparison with FeN-SBC, the better catalytic performance of FeN-RBC was mainly ascribed to its higher amount of pyridine-N and Fe0, and more reactive active sites (such as CO group and Fe-N sites). Density functional theory calculations indicated the greater adsorption energy and Bader charge, more stable Fe-O bond, more easily broken OO bond in FeN-RBC/PMS, which demonstrated the stronger electron transfer capacity between FeN-RBC and PMS. To encapsulate, our study provided an efficient and dependable method for the simultaneous elimination of ARGs and ARB in water.

A carboxylate linker strategy mediated densely accessible Fe-N4 sites for enhancing oxygen electroreduction in Zn-air batteries

Iron-nitrogen-carbon single-atom catalysts derived from zeolitic-imidazolate-framework-8 (ZIF-8) have presented its great potential for the oxygen reduction reaction (ORR) in Zn-air batteries (ZABs). However, due to insufficient active Fe-N sites, its ORR activity is inferior to Pt-based catalysts. Herein, a carboxylate (OAc) linker strategy is proposed to design a ZIF-8-derived FeNCOAc catalyst with abundant accessible Fe-N4 single-atom sites. Except that imidazole groups can coordinate with Fe ions, the OAc linker on the unsaturated coordination Zn nodes can anchor and coordinate with more Fe ions, resulting in a significant increase in Fe-N4 site density. Meanwhile, the corrosion of carbon skeleton by OAc oxidation during heat-treatment leads to improved porosity of catalyst. Benefitting from the highly dense Fe-N4 sites and hierarchical pores, the FeNCOAc endows superior performance in alkaline medium (E1/2 = 0.906 V), which is confirmed by density functional theory calculation results. Meanwhile, the assembled liquid ZAB delivers a favorable peak power density of 173.9 mW cm−2, and a high specific capacity of 770.9 mAh g−1 as well as outstanding durability. Besides, the solid-state ZAB also shows outstanding discharge performance.

Nitrogen-doped carbon supported iron nanoparticles for mild catalytic hydrocracking of Xilinguole lignite

Cleaving C-O bridged bonds of lignite via catalytic hydrocracking (CHC) is an effective method to produce chemicals and clean fuels. Herein, a nitrogen-doped carbon supported Fe catalyst was developed by using a one-pot method for CHC of Xilinguole lignite (XL) and its related model compounds. The doped nitrogen enhanced the interaction between Fe and N species to form Fe-N sites and favored forming smaller Fe/Fe3C nanocrystals, which played a crucial role in CHC performance. Toluene and phenol were produced from CHC of benzyl phenyl ether (BPE) with high yield and selectivity at 250 °C over the optimal catalyst with 4% Fe, without hydrogenation products. The Fe-based catalyst activated both H2 and isopropanol to generate hydrogen radicals for cleaving C-O bridged bonds. The CHC of XL under different temperature and time showed that the yields of oil, asphaltene and preasphaltene were obviously promoted under 325 °C, 1 MPa, and 6 h, and they had much higher H/C ratio but remarkably lower O/C ratio, resulting in much higher heating values (28.19–36.90 MJ/kg) than XL. Phenols were the major group component with relative content of 53.6 wt% in oil from CHC, and the asphaltene and preasphaltene from CHC had obviously lower molecular weights, which could attributed to depolymerization of C-O bridged bonds in the XL macromolecular structures over the catalyst.

Embedded iron and nitrogen co-doped carbon quantum dots within g-C3N4 as an exceptional PMS photocatalytic activator for sulfamethoxazole degradation: The key role of Fe[sbnd]N bridge

The covalent modification of graphite-phase carbon nitride (g-C3N4) by carbon quantum dots (CQDs) is a promising way to improve its photocatalytic performance. Although CQDs can act as charge mediator for electrons storage and transfer, it is crucial to construct efficient interfaces, which serves as active sites for tight connect with g-C3N4 and fast release of electrons. Herein, a novel iron and nitrogen co-doped carbon quantum dots (Fe, N-CQDs) assembled g-C3N4 composite (FNCCN) was constructed via FeN bridge by hydrothermal and thermal polymerization methods. The FNCNN rivaled popular nitrogen-doped carbon quantum dots (N-CQDs) combined with g-C3N4 composites for peroxymonosulfate (PMS) activation and degradation of sulfamethoxazole (SMX). The SMX degradation rate (0.0963 min−1) is 5.38 and 3.15 times higher than that of g-C3N4 and N-CQDs/g-C3N4. The characterization and DFT calculation results suggest that Fe, N-CQDs was successfully incorporated into carbon matrix of g-C3N4 via FeN covalent bond, which joints the two counterparts closely and creates electron transport channels for higher electrons transfer efficiency. The FeN coordinated structure promotes PMS reduction on Fe2+ of FeN sites for HO and SO4- production and expedited photo carries separation through Fe3+/Fe2+ cycling. In addition, the degradation efficiency, ROS identification, EPR test and degradation pathway of SMX was determined, and the intermediate toxicity of degradation products was predicted. This work constructed a tight atomic-level connection between hydrophobic g-C3N4 and hydrophilic CQDs, which improved an effective strategy for accelerating electron transport and efficient photocatalytic activation of PMS.

Regulating the frontier orbital of iron phthalocyanine with nitrogen doped carbon nanosheets for improving oxygen reduction activity.

Iron phthalocyanine (FePc) has attracted widespread attention for its tunable electronic structure. However, the Fe-N sites suffer from undesirable oxygen reduction activity due to the symmetric geometries. A suitable substrate was thus needed to induce electron redistribution around Fe-N to improve the activity. Herein, ultrathin nitrogen-doped carbon nanosheets (N-CNSs) were prepared by a simple high temperature pyrolysis. Then iron phthalocyanine was loaded on the ultrathin nitrogen-doped carbon nanosheets (FePc@N-CNSs) by a low-cost and simple solution method. This composite catalyst shows an excellent ORR activity with a half potential of 0.88 V, an onset potential of 0.99 V and durability superior to commercial Pt/C. When used as an air cathode catalyst for rechargeable zinc-air batteries, FePc@N-CNS modified batteries outperform Pt/C + RuO2 modified batteries with higher power density and superior constant current charge-discharge cycling stability of 37 hours. The regulated electronic structure of FePc by the N-CNS substrate was revealed further by DFT calculations, which explained the enhanced adsorption of the active center to the intermediates and the increased ORR performance.

Recent increases in annual, seasonal, and extreme methane fluxes driven by changes in climate and vegetation in boreal and temperate wetland ecosystems.

Climate warming is expected to increase global methane (CH4 ) emissions from wetland ecosystems. Although insitu eddy covariance (EC) measurements at ecosystem scales can potentially detect CH4 flux changes, most EC systems have only a few years of data collected, so temporal trends in CH4 remain uncertain. Here, we use established drivers to hindcast changes in CH4 fluxes (FCH4 ) since the early 1980s. We trained a machine learning (ML) model on CH4 flux measurements from 22 [methane-producing sites] in wetland, upland, and lake sites of the FLUXNET-CH4 database with at least two full years of measurements across temperate and boreal biomes. The gradient boosting decision tree ML model then hindcasted daily FCH4 over 1981-2018 using meteorological reanalysis data. We found that, mainly driven by rising temperature, half of the sites (n = 11) showed significant increases in annual, seasonal, and extreme FCH4 , with increases in FCH4 of ca. 10% or higher found in the fall from 1981-1989 to 2010-2018. The annual trends were driven by increases during summer and fall, particularly at high-CH4 -emitting fen sites dominated by aerenchymatous plants. We also found that the distribution of days of extremely high FCH4 (defined according to the 95th percentile of the daily FCH4 values over a reference period) have become more frequent during the last four decades and currently account for 10-40% of the total seasonal fluxes. The share of extreme FCH4 days in the total seasonal fluxes was greatest in winter for boreal/taiga sites and in spring for temperate sites, which highlights the increasing importance of the non-growing seasons in annual budgets. Our results shed light on the effects of climate warming on wetlands, which appears to be extending the CH4 emission seasons and boosting extreme emissions.

Paleoecology of vegetation changes associated with a prehistoric earthquake at Serpentine Fen, southwestern British Columbia, Canada

A sedimentary exposure near the mouth of Serpentine River, about 25 km southeast of Vancouver, British Columbia, records evidence of a large earthquake that happened about 2000 years ago. The evidence includes sand dykes injected into late Holocene peat and mud. Vegetation changes based on pollen analysis and radiocarbon-dated wood match sedimentary changes at the Serpentine Fen site. A shift from herbaceous to woody peat is matched by a dramatic peak (∼45%) in pollen of Myrica shrubs, indicating uplift and a vegetation shift to drier shrubland from fen, also incorporating detrital spruce wood (Picea). At the top of the woody peat, Myrica pollen disappears and intertidal mud with Triglochin-type pollen increases, indicating subsidence and establishment of an intertidal environment. The section above the woody peat shows increasing amounts of halophyte pollen, especially Chenopodiaceae (or Amaranthaceae) which reaches values up to 60%, and scattered dinoflagellate cysts, indicative of a continued tidal influence. The combined evidence of uplift and subsidence over a short interval is rare at most sites in south-coastal British Columbia.

Paludiculture can support biodiversity conservation in rewetted fen peatlands

Paludiculture, the productive use of wet or rewetted peatlands, offers an option for continued land use by farmers after rewetting formerly drained peatlands, while reducing the greenhouse gas emissions from peat soils. Biodiversity conservation may benefit, but research on how biodiversity responds to paludiculture is scarce. We conducted a multi-taxon study investigating vegetation, breeding bird and arthropod diversity at six rewetted fen sites dominated by Carex or Typha species. Sites were either unharvested, low- or high-intensity managed, and were located in Mecklenburg-Vorpommern in northeastern Germany. Biodiversity was estimated across the range of Hill numbers using the iNEXT package, and species were checked for Red List status. Here we show that paludiculture sites can provide biodiversity value even while not reflecting historic fen conditions; managed sites had high plant diversity, as well as Red Listed arthropods and breeding birds. Our study demonstrates that paludiculture has the potential to provide valuable habitat for species even while productive management of the land continues.

Resolving the Carbon‐Climate Feedback Potential of Wetland CO2 and CH4 Fluxes in Alaska

AbstractBoreal‐Arctic regions are key stores of organic carbon (C) and play a major role in the greenhouse gas balance of high‐latitude ecosystems. The carbon‐climate (C‐climate) feedback potential of northern high‐latitude ecosystems remains poorly understood due to uncertainty in temperature and precipitation controls on carbon dioxide (CO2) uptake and the decomposition of soil C into CO2 and methane (CH4) fluxes. While CH4 fluxes account for a smaller component of the C balance, the climatic impact of CH4 outweighs CO2 (28–34 times larger global warming potential on a 100‐year scale), highlighting the need to jointly resolve the climatic sensitivities of both CO2 and CH4. Here, we jointly constrain a terrestrial biosphere model with in situ CO2 and CH4 flux observations at seven eddy covariance sites using a data‐model integration approach to resolve the integrated environmental controls on land‐atmosphere CO2 and CH4 exchanges in Alaska. Based on the combined CO2 and CH4 flux responses to climate variables, we find that 1970‐present climate trends will induce positive C‐climate feedback at all tundra sites, and negative C‐climate feedback at the boreal and shrub fen sites. The positive C‐climate feedback at the tundra sites is predominantly driven by increased CH4 emissions while the negative C‐climate feedback at the boreal site is predominantly driven by increased CO2 uptake (80% from decreased heterotrophic respiration, and 20% from increased photosynthesis). Our study demonstrates the need for joint observational constraints on CO2 and CH4 biogeochemical processes—and their associated climatic sensitivities—for resolving the sign and magnitude of high‐latitude ecosystem C‐climate feedback in the coming decades.

Fe-N and Fe-P dual active centers in MOF-derived carbon electrode for efficient capacitive deionization: Abundant defects and superior electrochemical properties

Carbon-based compounds play a significant role in achieving efficient capacitive deionization (CDI) desalination. However, the adsorption capacity is usually restricted by single spatial structures and limited number of ion adsorption sites. Heteroatom doping, especially multiple doping is an effective strategy to augment the surface functionalities of electrodes to improve the capacitive activity. In this work, Fe, N, P tri-doped hierarchically porous carbon (FeNPCs) were successfully fabricated via a facile one-step pyrolysis procedure. The FeNPC30 electrode demonstrated an outstanding electrosorption capacity of 40.42 mg g−1 within 15 min at 1.2 V and good cyclic regeneration capability with little decrease in charge storage during 200 charge/discharge cycles. The systematic results revealed that a reasonable ratio of Fe, N, and P yielded a synergistic effect, which not only improved the defective level and hydrophilicity, but enhanced the specific capacitance and decreased the charge transfer resistance, resulting in superior adsorption capacity and rate. The unique coordination structures of Fe-N and Fe-P modulated the charge density distribution and served as additional active sites for ions trapping, thus improving the desalination performance. This work gives deep insight into Fe-N and Fe-P dual active sites in CDI and provides a new perspective on multiple heteroatoms doped electrodes.

Single Atom and Hierarchical Pore Aerogel Confinement Strategy for Low-platinum Fuel CellSingle Atom and Hierarchical Pore Aerogel Confinement Strategy for Low-platinum Fuel Cell.

Achieving high catalytic performance through the lowest possible content of platinum (Pt) is the key to cost reduction of proton exchange membrane fuel cells (PEMFCs). However, lowering the Pt loading in PEMFCs leads to high mass transport resistance of oxygen originated from the limited accessible active sites, and cause less stability of loaded ultrafine Pt nano-catalyst due to substantial size growth in long-term operations. Herein, we design new Pt-metal/metal-N-C aerogel catalyst that substantially reduces oxygen-related mass transport resistance and has long-term durability. The tailor of the Fe-N-C aerogel support with hierarchical and interconnecting pores enable a low local oxygen transport resistance (0.18 s/cm) for fuel cell with ultra-low Pt loading (50 ± 5μg Pt /cm2 ). Chemical confinement of Fe-N sites in Fe-N-C aerogel ensure high stability of the loaded-Pt both in the processes of high temperature synthesis up to 1000°C and practical application as fuel cell catalyst. The ultra-low Pt fuel cell displays a low voltage loss of 8mV at 0.80 A/cm2 and unchanged electrochemical surface area after 60, 000 cycles of accelerated durability test. The allied of hierarchical pore, aerogel and single atom can fully reflect their structural advantages and expand the understanding for the synthesis of advanced fuel cell catalysts. This article is protected by copyright. All rights reserved.

Comparison of GHG emissions from annual crops in rotation on drained temperate agricultural peatland with production of reed canary grass in paludiculture using an LCA approach

Drained peat soils contribute significantly to global human-caused CO2 emissions and reducing peat degradation via rewetting is high on the political agenda. Ceasing agricultural activities on rewetted soils might lead to land owner resistance and high societal expenses to compensate farmers. Continued biomass production adapted for wet conditions on peat soils potentially minimizes these costs and helps supplying the growing demand for e.g. materials, fuels and feed. Here we used a life cycle assessment approach (cradle to farm gate) to investigate the greenhouse gas (GHG) emissions related to three cases by applying IPCC (Intergovernmental Panel on Climate Change) emission factors and specific site conditions at a bog and a fen site that represent widely distributed temperate peat soils. Besides soil emissions, upstream emissions from input, operational emissions and emission related to rewetting construction work were included. The analyzed systems were deeply drained cash cropping on agricultural bog (potatoes (Solanum tuberosum L.), spring barley (Hordeum vulgare L.) and oat (Avena sativa L.), permanent Reed canary grass (RCG) (Phalaris arundinacea L.) production on non-drained bog and permanent RCG production on shallow-drained fen. The annual mean water table depths (WTD) were −70, −38 (estimated) and −13 cm, respectively. Results showed estimated GHG emissions of 40.5, 26.1 and 20.6 Mg CO2eq ha−1, respectively, corresponding to a 35% GHG reduction for the non-drained bog case as compared to the drained bog case, despite that the obtained WTD due to ceased drainage did not adhere to the IPCC rewetting threshold of −30 cm. Emissions related to crop management represented 7, 14 and 19% of total emissions. In the RCG cultivation on fen case, the WTD were controlled primarily by the water table of the nearby stream and total GHG emissions were even lower as compared to the RCG production on the non-drained bog reflecting the difference in WTD. Rewetting projects need to include careful knowledge of the specific peat area to foresee the actual reduction potential.

Effect of boron and nitrogen modulation in metal atoms anchoring on flower-like carbon superstructure for efficient ammonia electrosynthesis

Electrocatalytic nitrogen reduction reaction (NRR) is regarded as an ideal alternative technology to the conventional ammonia synthesis. The best way to improve the yield and Faraday efficiency (FE) of the electrocatalytic NRR is the development of low-cost, stable, and efficient catalysts. Herein, a boron-based Zn-metal–organic framework is used to prepare metal atoms (Fe) anchored on B/N co-doped carbon (Fe-B/N-C) as efficient NRR catalysts. Fe-B/N-C shows an excellent NRR performance (with the maximum ammonia yield of 100.1 μg·h−1·mgcat-1 and the maximum FE of 23.0%), which are superior to most of the reported NRR catalysts. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) demonstrate that Fe atoms can achieve an atomic-level dispersion on the flower cluster-like superstructure and coordinate with N atoms to form Fe-N sites. Theoretical calculations show that in the Fe-N4-B, the boron atom in the substrate can reduce the energy barrier of both the nitrogen activation and the rate-determining step (RDS) of NRR, and the distal pathway of association mechanism is more favorable. This work provides a new insight into the effect of dual-atom doping on the NRR process and kinetics, which is important to the development of high-performance NRR catalysts.

Nearly zero peroxydisulfate consumption for persistent aqueous organic pollutants degradation via nonradical processes supported by in-situ sulfate radical regeneration in defective MIL-88B(Fe)

The porous defective MIL-88B(Fe) with abundant oxygen vacancies and Fe-N sites was fabricated to accomplish nearly zero peroxydisulfate (PDS) consumption for persistent bisphenol A (BPA) degradation via electron-transfer pathway (ETP). Interestingly, the generated sulfates during ETP were oxidized to yield the confined sulfate radicals and to accomplish the peroxydisulfate regeneration in the fine-tuned MIL-88B(Fe), which was verified by series experiments and DFT calculations. Further studies suggested that the optimal De-MIL-88B(Fe)-1.25 catalyst achieved the persistent nonradical reactions for BPA decomposition under visible light irradiation with both low input and low consumption of PDS. It was the first case to achieve nearly zero PDS consumption for emerging pollutants elimination, which provided new strategy to design and tune defective metal-organic frameworks for the purpose of reducing the stoichiometry between PDS and contaminants for nearly zero PDS consumption.

Modeled production, oxidation, and transport processes of wetland methane emissions in temperate, boreal, and Arctic regions.

Wetlands are the largest natural source of methane (CH4 ) to the atmosphere. The eddy covariance method provides robust measurements of net ecosystem exchange of CH4 , but interpreting its spatiotemporal variations is challenging due to the co-occurrence of CH4 production, oxidation, and transport dynamics. Here, we estimate these three processes using a data-model fusion approach across 25 wetlands in temperate, boreal, and Arctic regions. Our data-constrained model-iPEACE-reasonably reproduced CH4 emissions at 19 of the 25 sites with normalized root mean square error of 0.59, correlation coefficient of 0.82, and normalized standard deviation of 0.87. Among the three processes, CH4 production appeared to be the most important process, followed by oxidation in explaining inter-site variations in CH4 emissions. Based on a sensitivity analysis, CH4 emissions were generally more sensitive to decreased water table than to increased gross primary productivity or soil temperature. For periods with leaf area index (LAI) of ≥20% of its annual peak, plant-mediated transport appeared to be the major pathway for CH4 transport. Contributions from ebullition and diffusion were relatively high during low LAI (<20%) periods. The lag time between CH4 production and CH4 emissions tended to be short in fen sites (3 ± 2 days) and long in bog sites (13 ± 10 days). Based on a principal component analysis, we found that parameters for CH4 production, plant-mediated transport, and diffusion through water explained 77% of the variance in the parameters across the 19 sites, highlighting the importance of these parameters for predicting wetland CH4 emissions across biomes. These processes and associated parameters for CH4 emissions among and within the wetlands provide useful insights for interpreting observed net CH4 fluxes, estimating sensitivities to biophysical variables, and modeling global CH4 fluxes.