Localized Traps Limited Recombination in Lead Bromide Perovskites

Traps exert an omnipotent influence over the performance of halide perovskite optoelectronic devices. A clear understanding of the origin and nature of the traps in halide perovskites is the key to controlling them and realizing optimal devices. Herein, the role of localized traps on the optical properties of lead bromide perovskite films is investigated. In the low‐temperature orthorhombic phase of CH₃NH₃PbBr₃ perovskite, band‐edge carrier dynamics exhibit a power‐law decay due to the presence of structural‐disorder‐induced localized traps, which has a depth of ≈40 meV. The continuous distribution of these localized traps gives rise to a broad sub‐band‐gap emission that becomes more prominent in thicker films with a larger trap density. The presence of this emission only from the hybrid organic–inorganic perovskites points to the vital role of organic dipoles in localized trap states formation. This study explicates the nature of these localized traps as well as their nontrivial role in carrier recombination kinetics, which is of fundamental importance in perovskites optoelectronics.     

NH4 + transport system of a psychrophilic marine bacterium, Vibrio sp. strain ABE-1

NH₄ ⁺ transport system of a psychrophilic marine bacterium Vibrio sp. strain ABE-1 (Vibrio ABE-1) was examined by measuring the uptake of [¹⁴C]methylammonium ion (¹⁴CH₃NH^{3 +}) into the intact cells. ¹⁴CH₃NH₃ ⁺ uptake was detected in cells grown in medium containing glutamate as the sole nitrogen source, but not in those grown in medium containing NH₄Cl instead of glutamate. Vibrio ABE-1 did not utilize CH₃NH₃ ⁺ as a carbon or nitrogen source. NH₄Cl and nonradiolabeled CH₃NH₃ ⁺ completely inhibited ¹⁴CH₃NH₃ ⁺ uptake. These results indicate that ¹⁴CH₃NH₃ ⁺ uptake in this bacterium is mediated via an NH₄ ⁺ transport system and not by a specific carrier for CH₃NH₃ ⁺. The respiratory substrate succinate was required to drive ¹⁴CH₃NH₃ ⁺ uptake and the uptake was completely inhibited by KCN, indicating that the uptake was energy dependent. The electrochemical potentials of H⁺ and/or Na⁺ across membranes were suggested to be the driving forces for the transport system because the ionophores carbonylcyanide m-chlorophenylhydrazone and monensin strongly inhibited uptake activities at pH 6.5 and 8.5, respectively. Furthermore, KCl activated ¹⁴CH₃NH₃ ⁺ uptake. The ¹⁴CH₃NH₃ ⁺ uptake activity of Vibrio ABE-1 was markedly high at temperatures between 0° and 15°C, and the apparent K _m value for CH₃NH₃ ⁺ of the uptake did not change significantly over the temperature range from 0° to 25°C. Thus, the NH₄ ⁺ transport system of this bacterium was highly active at low temperatures. Received: August 1, 1998 / Accepted: October 8, 1998     

Stable Inverted Planar Perovskite Solar Cells with Low‐Temperature‐Processed Hole‐Transport Bilayer

Low‐temperature‐processed perovskite solar cells (PSCs), which can be fabricated on rigid or flexible substrates, are attracting increasing attention because they have a wide range of potential applications. In this study, the stability of reduced graphene oxide and the ability of a poly(triarylamine) underlayer to improve the quality of overlying perovskite films to construct hole‐transport bilayer by means of a low‐temperature method are taken advantage of. The bilayer is used in both flexible and rigid inverted planar PSCs with the following configuration: substrate/indium tin oxide/reduced graphene oxide/polytriarylamine/CH₃NH₃PbI₃/PCBM/bathocuproine/Ag (PCBM = [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester). The flexible and rigid PSCs show power conversion efficiencies of 15.7 and 17.2%, respectively, for the aperture area of 1.02 cm². Moreover, the PSC based the bilayer shows outstanding light‐soaking stability, retaining ≈90% of its original efficiency after continuous illumination for 500 h at 100 mW cm^?2.     

Efficient Solution‐Processed Bulk Heterojunction Perovskite Hybrid Solar Cells

Efficient conventional bulk heterojunction (BHJ) perovskite hybrid solar cells (pero‐HSCs) solution‐processed from a composite of CH₃NH₃PbI₃ mixed with PC₆₁BM ([6,6]‐phenyl‐C61‐butyric acid methyl ester), where CH₃NH₃PbI₃ acts as the electron donor and PC₆₁BM acts as the electron acceptor, are reported for the first time. The efficiency of 12.78% is twofold enhancement in comparison with the conventional planar heterojunction pero‐HSCs (6.90%) fabricated by pristine CH₃NH₃PbI₃. The BHJ pero‐HSCs are further optimized by using PC₆₁BM/TiO₂ bi‐electron‐extraction‐layer (EEL), which are both solution‐processed and then followed with low‐temperature thermal annealing. Due to higher electrical conductivity of PC₆₁BM over that of TiO₂, an efficiency of 14.98%, the highest reported efficiency for the pero‐HSCs without incorporating high‐temperature‐processed mesoporous TiO₂ and Al₂O₃ as the EEL and insulating scaffold, is observed from PC₆₁BM modified BHJ pero‐HSCs. Thus, the findings provide a simple way to approach high efficiency low‐cost pero‐HSCs.     

Unveiling the Low‐Temperature Pseudodegradation of Photovoltaic Performance in Planar Perovskite Solar Cell by Optoelectronic Observation

The time evolution of the current–voltage characteristic of planar heterojunction perovskite solar cell (PSC) is studied within an operating temperature range of 200–325 K. The photovoltaic (PV) performance of PSC is found to be influenced by five carrier transport pathways, which strongly depend on operating temperature and light illumination. At low temperature, a severe degradation of PV performance is presented but temporary. This is attributed to ion accumulation at the TiO₂/CH₃NH₃PbI₃ and hole transport material/CH₃NH₃PbI₃ interfacial regions, as an origin of screening effect of built‐in field, evidenced by the low external quantum efficiency (EQE). By light illumination at open‐circuit, a steady PV performance will be reached and the stabilization time increases with decreasing temperature. The recovery of PV performance is attributed to ion diffusion in CH₃NH₃PbI₃ layer in the absence of electric field. The EQE observations indicate that photogenerated carriers are separated and collected efficiently after a long time light illumination due to a reduction of the screening effect. At high temperature, because of the low ion density at interfacial regions, the PV performance shows a quick response to light. These findings may help understanding of the mechanism of temperature‐dependent photogenerated carrier transport in the PSC.     

Synthesis and spectroscopic properties of some new seven-coordinate thioacetamide complexes of molybdenum(II) and tungsten(II)

The compounds [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of SC(NH₂)Me in CH₂Cl₂ at room temperature to initially give the acetonitrile substituted products [MI₂(CO)₃(NCMe)- {SC(NH₂)Me}] which was isolated for M = W. However, the molybdenum complex rapidly dimerizes with loss of acetonitrile to give the iodide-bridged compound [Mo(σ-I)I(CO)₃ {SC(NH₂)Me}]₂. The tungsten complex does not appear to dimerize, even after stirring at room temperature for 72 h in CH₂Cl₂. Two equivalents of thioacetamide react with [MI₂- (CO)₃(NCMe)₂] in CH₂Cl₂ at room temperature to give the new bisthioacetamide compounds [MI₂- (CO)₃{SC(NH₂)Me}₂] via displacement of the labile acetonitrile ligands. The low temperature (−70 °C) ¹³C NMR spectrum of [WI₂(CO)₃{SC(NH₂)Me}₂] indicates that the geometry of the complex is capped octahedral with a carbonyl ligand in the unique capping position.     

Theoretical study on the functionalization of BC2N nanotube with amino groups

Using density functional theory calculations, we investigated properties of a functionalized BC₂N nanotube with NH₃ and five other NH₂-X molecules in which one of the hydrogen atoms of NH₃ is substituted by X = ?CH₃, ?CH₂CH₃, ?COOH, ?CH₂COOH and ?CH₂CN functional groups. It was found that NH₃ can be preferentially adsorbed on top of the boron atom, with adsorption energy of ?12.0 kcal mol^?1. The trend of adsorption-energy change can be correlated with the trend of relative electron-withdrawing or -donating capability of the functional groups. The adsorption energies are calculated to be in the range of ?1.8 to ?14.2 kcal mol^?1, and their relative magnitude order is found as follows: H₂N(CH₂CH₃) > H₂N(CH₃) > NH₃ > H₂N(CH₂COOH) > H₂N(CH₂CN) > H₂N(COOH). Overall, the functionalization of BC₂N nanotube with the amino groups results in little change in its electronic properties. The preservation of electronic properties of BC₂N coupled with the enhancement of solubility renders their chemical modification with either NH₃ or amino functional groups to be a way for the purification of BC₂N nanotubes.     

Efficient Perovskite Solar Cells Fabricated by Co Partially Substituted Hybrid Perovskite

In the past years, hybrid perovskite materials have attracted great attention due to their superior optoelectronic properties. In this study, the authors report the utilization of cobalt (Co²⁺) to partially substitute lead (Pb²⁺) for developing novel hybrid perovskite materials, CH₃NH₃Pb_1‐xCo_xI₃ (where x is nominal ratio, x = 0, 0.1, 0.2 and 0.4). It is found that the novel perovskite thin films possess a cubic crystal structure with superior thin film morphology and larger grain size, which is significantly different from pristine thin film, which possesses the tetragonal crystal structure, with smaller grain size. Moreover, it is found that the 3d orbital of Co²⁺ ensures higher electron mobilities and electrical conductivities of the CH₃NH₃Pb_1‐xCo_xI₃ thin films than those of pristine CH₃NH₃Pb₄ thin film. As a result, a power conversion efficiency of 21.43% is observed from perovskite solar cells fabricated by the CH₃NH₃Pb_0.9Co_0.1I₃ thin film. Thus, the utilization of Co, partially substituting for Pb to tune physical properties of hybrid perovskite materials provides a facile way to boost device performance of perovskite solar cells.     

Exploring the Limiting Open‐Circuit Voltage and the Voltage Loss Mechanism in Planar CH3NH3PbBr3 Perovskite Solar Cells

Perovskite solar cells based on CH₃NH₃PbBr₃ with a band gap of 2.3 eV are attracting intense research interests due to their high open‐circuit voltage (V_oc) potential, which is specifically relevant for the use in tandem configuration or spectral splitting. Many efforts have been performed to optimize the V_oc of CH₃NH₃PbBr₃ solar cells; however, the limiting V_oc (namely, radiative V_oc:V_oc,rad) and the corresponding ΔV_oc (the difference between V_oc,rad and V_oc) mechanism are still unknown. Here, the average V_oc of 1.50 V with the maximum value of 1.53 V at room temperature is achieved for a CH₃NH₃PbBr₃ solar cell. External quantum efficiency measurements with electroluminescence spectroscopy determine the V_oc,rad of CH₃NH₃PbBr₃ cells with 1.95 V and a ΔV_oc of 0.45 V at 295 K. When the temperature declines from 295 to 200 K, the obtained V_oc remains comparably stable in the vicinity of 1.5 V while the corresponding ΔV_oc values show a more significant increase. Our findings suggest that the V_oc of CH₃NH₃PbBr₃ cells is primarily limited by the interface losses induced by the charge extraction layer rather than by bulk dominated recombination losses. These findings are important for developing strategies how to further enhance the V_oc of CH₃NH₃PbBr₃‐based solar cells.     

Bioscrubber treatment of exhaust air from intensive pig production: Case study in northern Germany at mild climate condition

Treatment by field‐scale bioscrubber of exhaust air, including ammonia (NH₃) and the greenhouse gases methane (CH₄), nitrous oxide (N₂O), and carbon dioxide (CO₂), from 13 intensive pig production houses located in northern Germany were investigated in 2013 and 2015. NH₃ removal efficiencies varied between 35 and 100% with an overall average value of 79% under the NH₃ inlet fluctuations from 34 to 755 g d^?1 m^?3 in both 2013 and 2015. Results of the electron microscopic analyses demonstrated that the bacteria Nitrosomonas sp. and methanotrophs type I were the dominant NH₃ and CH₄ oxidizers, respectively. However, overall average removal efficiencies of CH₄ was approximately zero, which means CH₄ is hard to remove in bioscrubbers under normal operation. The pH of recirculation water in the bioscrubber varied from 6.1 to 8.1, and the bioscrubbers with low pH values (<7.0) had high NH₃ removal efficiencies (>79%). Electrical conductivity was commonly used to diagnose the bioscrubbers’ performance; in the present study, electrical conductivity presented a significant linear relationship with dissolved inorganic nitrogen, which indicates the performance stability of the 13 selected bioscrubbers.     

Microbial processes influencing methane emission from rice fields

Irrigated rice fields are an important source of atmospheric methane. In order to improve our understanding of the controlling processes, we measured in situ CH₄ emission and CH₄ oxidation in an Italian rice field in 1998 and 1999, and studied CH₄ production in soil and root samples. The CH₄ emission rates were correlated with diurnal temperature variations and showed pronounced seasonal and interannual variations. The contribution of CH₄ oxidation to total CH₄ flux, determined by specific inhibition with difluoromethane, decreased from 40% at the beginning to zero at the end of the season. The stable carbon isotopic composition of the emitted CH₄ also decreased. The CH₄‐oxidizing bacteria probably became limited by nitrogen as indicated by the seasonal decrease of NH₄⁺. Thus, CH₄ oxidation had little effect on CH₄ emission. Methane production on rice roots was relatively constant over the season. Methane production in soil slowly increased after flooding and was highest in the middle of the season. Pore water concentrations of CH₄ showed a similar seasonal pattern. In 1999, CH₄ production increased later in the season and reached lower rates than in 1998. An additional drainage in 1999 resulted in higher ferric iron concentrations, higher soil redox potentials and lower acetate concentrations. As a result, acetate‐utilizing methanogens were probably out‐competed by iron‐reducers so that a larger percentage of [2–¹⁴C]acetate was converted to ¹⁴CO₂ instead of ¹⁴CH₄. The residual CH₄ production was relatively low and was mainly due to H₂/CO₂‐dependent methanogenesis. Experiments with radioactive bicarbonate and with methyl fluoride as specific inhibitor showed that the theoretical ratio of 7:3 of methanogenesis from acetate vs. H₂/CO₂ was only reached later in the season when total CH₄ production was at the maximum. In conclusion, our results give a mechanistic explanation for the intraseasonal and interannual differences in CH₄ emission.     

Relationships between Root Temperature and the Transport of Ammonium and Nitrate Ions by Italian and Perennial Ryegrass (Lolium multiflorum and Lolium perenne)

At root temperature below 14 C the absorption of ¹⁵N from NH₄⁺ greatly exceeded that from NO₂⁻ by tillers of Lolium multiflorum and Lolium perenne under conditions where pH, external concentration, plant N status, and pretreatment temperature were varied. There was a marked increase in the temperature sensitivity of NO₃⁻ transport below 14 C, irrespective of the temperature at which plants were grown previously. A marked increase in the temperature sensitivity was also seen for NH₄⁺ transport, but this occurred at the lower temperature of 10 C. Pretreatment of roots at 8 C lowered this still further to 5 C. Above and below these transition temperatures the Q₁₀ values for NO₃⁻ and NH₄⁺ transport were similar. Thus, the increased absorption of NH₄⁺ relative to NO₃⁻ at low temperatures seems to be related primarily to the difference in transition temperatures.     

Solvent Engineering Boosts the Efficiency of Paintable Carbon‐Based Perovskite Solar Cells to Beyond 14%

Carbon‐based hole transport material (HTM)‐free perovskite solar cells (PSCs) have shown much promise for practical applications because of their high stability and low cost. However, the efficiencies of this kind of PSCs are still relatively low, especially for the simplest paintable carbon‐based PSCs, in comparison with the organic HTM‐based PSCs. This can be imputed to the perovskite deposition methods that are not very suitable for this kind of devices. A solvent engineering strategy based on two‐step sequential method is exploited to prepare a high‐quality perovskite layer for the paintable carbon‐based PSCs in which the solvent for CH₃NH₃I (MAI) solution at the second step is changed from isopropanol (IPA) to a mixed solvent of IPA/Cyclohexane (CYHEX). This mixed solvent not only accelerates the conversion of PbI₂ to CH₃NH₃PbI₃ but also suppresses the Ostwald ripening process resulting in a high‐quality perovskite layer, e.g., pure phase, even surface, and compact capping layer. The paintable carbon‐based PSCs fabricated from IPA/CYHEX solvent exhibits a considerable enhancement in photovoltaic performance and performance reproducibility in comparison with that from pure IPA, especially on fill factor (FF), owing mainly to the better contact of perovskite/carbon interface, lower trap density in perovskite, higher light absorption ability, and faster charge transport of perovskite layer. As a result, the highest power conversion efficiency (PCE) of 14.38% is obtained, which is a record value for carbon‐based HTM‐free PSCs. Furthermore, a PCE of as high as 10% is achieved for the large area device (1 cm²), also the highest of its kind.     

The Effect of Hydrophobicity of Ammonium Salts on Stability of Quasi‐2D Perovskite Materials in Moist Condition

With the potential of achieving high efficiency and low production costs, perovskite solar cells (PSCs) have attracted great attention. However, their unstableness under moist condition has retarded the commercial development. Recently, 2D perovskites have received a lot of attention due to their high moisture resistance. In this work, four quasi 2D quasi perovskites are prepared, then their stability under moist condition is investigated. The surface morphology, crystal structure, optical properties, and photovoltaic performance are measured. Among the four quasi‐2D perovskites, (C₆H₅CH₂NH₃)₂(FA)₈Pb₉I₂₈ has the best performance: uniform and dense film, extremely well‐oriented crystal structure, strong absorption, and a high power conversion efficiency (PCE) of 17.40%. The aging tests show that quasi‐2D perovskites are more stable under moist conditions than FAPbI₃ is. The (C₆H₅CH₂NH₃)₂(FA)₈Pb₉I₂₈ quasi‐2D perovskite devices exhibit high humidity stability, maintaining 80% of the starting PCE after 500 h under 80% relative humidity. Compared with other quasi‐2D perovskites, (C₆H₅CH₂NH₃)₂(FA)₈Pb₉I₂₈ has the highest humidity stability, due to their strongest hydrophobicity from C₆H₅CH₂NH₃⁺. This work demonstrates that the properties of perovskite materials can be modified by adding different ammonium salts into FAPbI₃. Thus, by introducing ammonium salts with high hydrophobic properties the fabrication of highly efficient and stable 2D PSCs may be possible.     

Ammonium and Methylammonium Transport in Egeria densa Leaves in Conditions of Different H+ Pump Activity

Previous data in Egeria densa leaves demonstrated a strong inhibitory effect of Cs⁺ on passive K⁺ influx and on K⁺-induced, ATP-dependent electrogenic proton extrusion. In this paper we analyzed, using the same material, the effects of Cs⁺ on ammonium (NH₄⁺) and methylammonium (CH₃NH₃⁺) transport in order to elucidate whether a common transport system for K⁺ and NH₄⁺ could be demonstrated. The effects of Cs⁺ on NH₄⁺- and CH₃NH₃⁺-induced titratable H⁺ extrusion (–ΔH⁺) and on transmembrane electrical potential difference (E_m) in E. densa leaves were analyzed in parallel. All experiments were run either in the absence or presence of fusicoccin, corresponding to low or high H⁺-ATPase activity and membrane hyperpolarization and leading, in this material, to respectively active or passive transport of K⁺. The results suggest the presence in E. densa leaves of two distinct pathways for NH₄⁺ uptake: one in common with NH₄⁺ and (with lower affinity) CH₃NH₃⁺, insensitive to Cs⁺, and a second system, operating at higher H⁺-ATPase activity and E_m hyperpolarization, strongly inhibited by Cs⁺ and impermeable to CH₃NH₃⁺. In agreement with this hypothesis, Xenopus laevis oocytes injected with the KAT1 RNA of Arabidopsis thaliana were permeable to K⁺ and NH₄⁺, but not to CH₃NH₃⁺.     

Flexible Lead‐Free Perovskite Oxide Multilayer Film Capacitor Based on (Na0.8K0.2)0.5Bi0.5TiO3/Ba0.5Sr0.5(Ti0.97Mn0.03)O3 for High‐Performance Dielectric Energy Storage

Flexible thin film dielectric capacitors with high energy storage density and a fast charging–discharging rate have attracted increasing attention as the development of microelectronics progresses toward flexibility and miniaturization. In this work, an all‐inorganic thin film dielectric capacitor with a multilayer structure based on (Na_0.8K_0.2)_0.5Bi_0.5TiO₃ and Ba_0.5Sr_0.5(Ti_0.97Mn_0.03)O₃ is designed and synthesized on a mica substrate. By optimizing the periodic number (N), concomitantly enhanced breakdown strength and large polarization difference are achieved in the film with N = 6, which contributes to the large energy density (W_rec) of 91 J cm^?3, high efficiency (η) of 68%, and fast discharging rate of 47.6 µs. The obtained energy density is the highest value up to now in flexible dielectric capacitors, including lead‐free and lead‐based inorganic films as well as organic dielectric films. Moreover, no obvious deterioration of the energy storage performance is observed in the wide ranges of working temperature (?50–200 °C), operating frequency (500 Hz to 30 kHz), and fatigue cycles (1–10⁸). Besides, the W_rec and η are ultra‐stable under various bending radii (R = 12–2 mm) and even after 10⁴ bending cycles at R = 4 mm, demonstrating an outstanding mechanical bending endurance. This excellent performance will allow the capacitor thrive in flexible microenergy storage systems.     

Greenhouse gas dynamics in boreal, littoral sediments under raised CO2 and nitrogen supply

SUMMARY 1. The effects of increasing CO₂ and nitrogen loading and of a change in water table and temperature on littoral CH₄, N₂O and CO₂ fluxes were studied in a glasshouse experiment with intact sediment cores including vegetation (mainly sedges), taken from a boreal eutrophic lake in Finland. Sediments with the water table held at a level of 0 or at ?15 cm were incubated in an atmosphere of 360 or 720 p.p.m. CO₂ for 18 weeks. The experiment included fertilisation with NO₃^– and NH₄⁺ (to a total 3 g N m^?2). 2. Changes in the water table and temperature strongly regulated sediment CH₄ and cCO₂ fluxes (community CO₂ release), but did not affect N₂O emissions. Increase in the water table increased CH₄ emissions but reduced cCO₂ release, while increase in temperature increased emissions of both CO₂ and CH₄. 3. The raised CO₂ increased carbon turnover in the sediments, such that cCO₂ release was increased by 16–26%. However, CH₄ fluxes were not significantly affected by raised CO₂, although CH₄ production potential (at 22 °C) of the sediments incubated at high CO₂ was increased. In the boreal region, littoral CH₄ production is more likely to be limited by temperature than by the availability of carbon. Raised CO₂ did not affect N₂O production by denitrification, indicating that this process was not carbon limited. 4. A low availability of NO₃^– did severely limit N₂O production. The NO₃^– addition caused up to a 100‐fold increase in the fluxes of N₂O. The NH₄⁺ addition did not increase N₂O fluxes, indicating low nitrification capacity in the sediments.     

Slow Organic‐to‐Inorganic Sub‐Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

Carrier dynamics in methylammonium lead halide (CH₃NH₃PbI_3–xCl_x) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long‐lived (>nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%–60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band‐edge photoluminescence (PL) decay only appears for excitation ≥2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon‐energy excitation yields slow dynamics consistent with negligible carrier trapping. Further, sub‐bandgap two‐photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub‐lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic‐to‐inorganic sub‐lattice equilibration timescale at optoelectronic‐relevant excitation energies.     

Isotopic insights into methane production,oxidation, and emissions in Arctic polygon tundra

Arctic wetlands are currently net sources of atmospheric CH₄. Due to their complex biogeochemical controls and high spatial and temporal variability, current net CH₄ emissions and gross CH₄ processes have been difficult to quantify, and their predicted responses to climate change remain uncertain. We investigated CH₄ production, oxidation, and surface emissions in Arctic polygon tundra, across a wet‐to‐dry permafrost degradation gradient from low‐centered (intact) to flat‐ and high‐centered (degraded) polygons. From 3 microtopographic positions (polygon centers, rims, and troughs) along the permafrost degradation gradient, we measured surface CH₄ and CO₂ fluxes, concentrations and stable isotope compositions of CH₄ and DIC at three depths in the soil, and soil moisture and temperature. More degraded sites had lower CH₄ emissions, a different primary methanogenic pathway, and greater CH₄ oxidation than did intact permafrost sites, to a greater degree than soil moisture or temperature could explain. Surface CH₄ flux decreased from 64 nmol m^?2 s^?1 in intact polygons to 7 nmol m^?2 s^?1 in degraded polygons, and stable isotope signatures of CH₄ and DIC showed that acetate cleavage dominated CH₄ production in low‐centered polygons, while CO₂ reduction was the primary pathway in degraded polygons. We see evidence that differences in water flow and vegetation between intact and degraded polygons contributed to these observations. In contrast to many previous studies, these findings document a mechanism whereby permafrost degradation can lead to local decreases in tundra CH₄ emissions.     

Simulated Nitrogen Deposition Reduces CH4 Uptake and Increases N2O Emission from a Subtropical Plantation Forest Soil in Southern China

To date, few studies are conducted to quantify the effects of reduced ammonium (NH₄ ⁺) and oxidized nitrate (NO₃ ⁻) on soil CH₄ uptake and N₂O emission in the subtropical forests. In this study, NH₄Cl and NaNO₃ fertilizers were applied at three rates: 0, 40 and 120 kg N ha⁻¹ yr⁻¹. Soil CH₄ and N₂O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0–20 cm depth was measured weekly to examine the regulation to soil CH₄ and N₂O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH₄ ⁺-N concentrations, but high levels of applied NH₄Cl and NaNO₃ fertilizers significantly increased soil NO₃ ⁻-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH₄ uptake, but significantly promoted soil N₂O emission by 403% to 762%. Furthermore, NH₄ ⁺-N fertilizer application had a stronger inhibition to soil CH₄ uptake and a stronger promotion to soil N₂O emission than NO₃ ⁻-N application. Also, both soil CH₄ and N₂O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH₄ uptake and N₂O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH₄ uptake and N₂O emission.