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Societal Impact Statement Increasing atmospheric nitrogen (N) deposition represents a major global change factor, but its long-term effect on tree growth and carbon (C) sequestration remains uncertain. Our manipulation experiment and meta-analysis reveal that N deposition in temperate and boreal forests promoted tree growth and the allocation of more C into wood than into leaves in China and worldwide. Thus, N deposition may increase forest C sequestration through enhanced wood production and distribution of C into stable sinks. In the context of achieving "Carbon Neutrality," understanding how N deposition affect long-term forest C sinks will help us with mitigation strategies under climate change. Increased nitrogen (N) deposition is driving many temperate and boreal forests in the Northern Hemisphere towards N saturation. However, it is uncertain how long-term N deposition affects tree growth and carbon (C) allocation in these forests. To investigate this, we treated temperate larch and mixed forests in northeastern China with N additions for 8 years. In addition, we collected data from 25 N-addition experiments in temperate and boreal forests worldwide to reveal the overall effects of N on tree growth and C allocation. Nitrogen additions significantly promoted total biomass increment by 24% in both study forests, with on average additional 8 kg C per kg N gain into woody biomass over the study period. Nitrogen additions increased the ratio of woody biomass increment to foliage litterfall production in the larch forest (by 34%). Literature data analysis also revealed greater N promotion on wood (24%) over foliage (9%) production. However, the positive effect on foliage diminished over time. These results combined imply that N deposition may promote tree growth in temperate and boreal regions and drive proportionally more photosynthate allocation into wood than leaves, thus may enhance forest C sequestration in the long run.

Background To assess the extent of belowground carbon transfer to ectomycorrhizal fungi in natural forests, we used δ13C and loge C/N measurements to calculate spatial dynamics of carbon movement into ectomycorrhizal sporocarps. Methods Fourteen broad-leaved trees were labeled with 13C-depleted CO2 from 2001–2005 in Switzerland and 13C traced into ectomycorrhizal sporocarps collected at different distances. We then used stepwise regressions on patterns of δ13C and loge C/N in ectomycorrhizal sporocarps as a function of distance (zone), solar radiation, fungal genus, and association type. Results CO2-labeled trees contributed 76 ± 5%, 36 ± 6%, and 19 ± 7% of sporocarp carbon at 0–6 m, 6–12 m, and 12–18 m from labeled trees, respectively. Literature estimates of hyphal development in different taxa did not correlate with carbon acquisition patterns. After drought in 2003, sporocarp loge C/N was low in 2004 and 13C-depleted carbon from elevated CO2 trees contributed less than in other years to sporocarps. In contrast, sporocarp loge C/N peaked in 2005 and contributions from elevated CO2 trees to the 6–12 m zone increased. Therefore, carbohydrate transport belowground decreased in 2004, reflecting plant allocation priorities, and increased in 2005. Sporocarp loge C/N varied less among years under elevated CO2 than elsewhere. Conclusions These patterns indicated that 1) belowground transport was influenced by climate and plant allocation, 2) root transport rather than ectomycorrhizal transport drove carbon spatial dynamics of ectomycorrhizal fungi, and 3) elevated CO2 decreased the sensitivity of belowground allocation to climatic fluctuations, suggesting improved drought resistance in a high-CO2 world.

Traditional strict separation of fungi into ecological niches as mutualist, par- asite or saprotroph is increasingly called into question. Sequences of assumed saprotrophs have been amplified from plant root interiors, and several saprotrophic genera can invade and interact with host plants in labo- ratory growth experiments. However, it is uncertain if root invasion by sapro- trophic fungi is a widespread phenomenon and if laboratory interactions mirror field conditions. Here, we focused on the widespread and speciose saprotrophic genus Mycena and performed (1) a systematic survey of their occurrences (in ITS1/ITS2 datasets) in mycorrhizal roots of 10 plant spe- cies, and (2) an analysis of natural abundances of 13C/15N stable isotope signatures of Mycena basidiocarps from five field locations to examine their trophic status. We found that Mycena was the only saprotrophic genus con- sistently found in 9 out of 10 plant host roots, with no indication that the host roots were senescent or otherwise vulnerable. Furthermore, Mycena basi- diocarps displayed isotopic signatures consistent with published 13C/15N profiles of both saprotrophic and mutualistic lifestyles, supporting earlier laboratory-based studies. We argue that Mycena are widespread latent invaders of healthy plant roots and that Mycena species may form a spec- trum of interactions besides saprotrophy also in the field.

Background. The spatial extent and timing of carbon fluxes from mature trees to ectomycorrhizal fungi associated with different hosts is challenging to assess in natural forests but could provide insights into carbon dynamics of fungi differing in exploration capabilities. Methods. We analyzed carbon movement into ectomycorrhizal sporocarps at the Swiss Forest Free-Air CO2 Enrichment (FACE) site in 2010 and 2011 during continuous labeling of five mature Picea abies (L.) H. Karst. with 13C-depleted CO2. Sporocarps were collected 0-6 m, 6-12 m, 12-18 m, and > 18 m from 13C-labeled trees. We then used stepwise regressions on patterns of 13C:12C ratios (δ13C) in ectomycorrhizal sporocarps as a function of distance (zone), solar radiation, fungal genus, and association type. Results. 18%, 10%, 40%, and 32% of ectomycorrhizal sporocarps were associated with conifers, broad-leaved trees, both, or of unknown association, respectively. Conifer-associated sporocarps derived 58 ± 7%, 41 ± 10%, and 20 ± 7% of their carbon from labeled trees in the 0-6 m, 6-12 m and 12-18 m zones, respectively, whereas other sporocarps in the 0-6 m zone only derived 34 ± 4% of their carbon from labeled trees. Sporocarp δ13C correlated positively with solar radiation for the 16-19 days prior to sporocarp harvest. Conclusions. These patterns indicated that (1) carbon spread further through conifer-associated mycorrhizal networks than through other fungal networks, and (2) carbon accumulation, storage, and transfer dynamics for sporocarp formation can take several weeks. Mature conifers supplied carbon to mycorrhizal fungi up to ~15 m from host trees.

Nitrogen (N) is one of the major nutrients limiting plant growth in terrestrial ecosystems. To avoid plant–microbe competition, previous studies on plant N uptake preference often used hydroponic experiments on fine roots of seedlings and demonstrated ammonium preference for conifer species; however, we lack information about N uptake and translocation in the field. In this paper, we described a method of in situ paired 15N labeling and reported the rates and time course of N uptake and translocation by mature trees in situ. We added 15N-enriched ammonium or nitrate, together with the nitrification inhibitor dicyandiamide, to paired Larix kaempferi (Lamb.) Carr (larch) trees from 30-, 40- and 50-year-old plantations. Fine roots, coarse roots, leaves and small branches were collected 2, 4, 7, 14 and 30 days after labeling. Nitrate uptake and translocation averaged 1.59 ± 0.16 μg 15N g−1 day−1, which is slightly higher than ammonium (1.08 ± 0.10 μg 15N g−1 day−1), in all tree organs. Nitrate contributed 50–78% to N uptake and translocation, indicating efficient nitrate use by larch in situ. We observed no age effect. We suggest that sampling leaves after 4 days of 15N labeling is sufficient to detect mature tree N uptake preference in situ. Whole-tree 15N-ammonium recovery equaled that of 15N-nitrate 30 days after 15N addition, implying the importance of both ammonium and nitrate to mature larch N use in the long run. We conclude that our method is promising for studying mature tree N uptake preference in situ and can be applied to other conifer and broadleaf species. We suggest using highly enriched 15N tracer to overcome soil dilution and a nitrification inhibitor to minimize ammonium transformation to nitrate. Our study revealed mature tree N preference in situ and demonstrated the strong contribution of nitrate toward mature larch growth on soils rich in nitrate.

Abstract Background Conifers partition different N forms from soil, including ammonium, nitrate, and dissolved organic N (DON), to sustain plant growth. Previous studies focused on inorganic N sources and specific amino acid forms using 15N labelling, but knowledge of the contribution of DON to mature conifers’ N uptake is still scarce. Here, we quantified the contribution of different N forms (DON vs. NH4+ vs. NO3−) to total N uptake, based on 15N natural abundance of plant and soil available N, in four mature conifers (Pinus koraiensis, Pinus sylvestris, Picea koraiensis, and Larix olgensis). Results DON contributed 31%, 29%, 28%, and 24% to total N uptake by Larix olgensis, Picea koraiensis, Pinus koraiensis, and Pinus sylvestris, respectively, whereas nitrate contributed 42 to 52% and ammonium contributed 19 to 29% of total N uptake for these four coniferous species. Conclusions Our results suggested that all four conifers could take up a relatively large proportion of nitrate, while DON was also an important N source for the four conifers. Given that DON was the dominant N form in study soil, such uptake pattern of conifers could be an adaptive strategy for plants to compete for the limited available N sources from soil so as to promote conifer growth and maintain species coexistence.

Efficient photoluminescence (PL) from silicon nanocrystal (SiNC) composites has important implications for emerging solar-collection technologies, yet a detailed understanding of the landscape of P...

Using a combination of density-gradient and analytical ultracentrifugation, we studied the photophysical profile of CsPbBr3 nanocrystal (NC) suspensions by separating them into size-resolved fracti...

Significance Peatlands store up to two-thirds of the world’s soil carbon, but this carbon may be released under warmer conditions, creating an important climate feedback. The belowground warming response of peatlands is particularly uncertain even though factors such as plant root growth regulate ecosystem water, carbon, and nutrient cycles. We studied how peatland fine roots respond to warming in a whole-ecosystem experiment. Fine-root growth increased dramatically, +130% for a degree of warming, primarily driven by soil drying. This warming response is 20 times stronger than in other ecosystem experiments, highlighting peatland vulnerability to warming. Our study elucidates large and rapid belowground changes that will affect peatlands of a warmer world and their ability to store carbon into the future., Belowground climate change responses remain a key unknown in the Earth system. Plant fine-root response is especially important to understand because fine roots respond quickly to environmental change, are responsible for nutrient and water uptake, and influence carbon cycling. However, fine-root responses to climate change are poorly constrained, especially in northern peatlands, which contain up to two-thirds of the world’s soil carbon. We present fine-root responses to warming between +2 °C and 9 °C above ambient conditions in a whole-ecosystem peatland experiment. Warming strongly increased fine-root growth by over an order of magnitude in the warmest treatment, with stronger responses in shrubs than in trees or graminoids. In the first year of treatment, the control (+0 °C) shrub fine-root growth of 0.9 km m−2 y−1 increased linearly by 1.2 km m−2 y−1 (130%) for every degree increase in soil temperature. An extended belowground growing season accounted for 20% of this dramatic increase. In the second growing season of treatment, the shrub warming response rate increased to 2.54 km m−2 °C−1. Soil moisture was negatively correlated with fine-root growth, highlighting that drying of these typically water-saturated ecosystems can fuel a surprising burst in shrub belowground productivity, one possible mechanism explaining the “shrubification” of northern peatlands in response to global change. This previously unrecognized mechanism sheds light on how peatland fine-root response to warming and drying could be strong and rapid, with consequences for the belowground growing season duration, microtopography, vegetation composition, and ultimately, carbon function of these globally relevant carbon sinks.

Nitrification is a crucial step in ecosystem nitrogen (N) cycling, but scaling up from plot-based measurements of gross nitrification to catchments is difficult. Here, we employed a newly developed method in which the oxygen isotope anomaly (Δ17O) of nitrate (NO3-) is used as a natural tracer to quantify in situ catchment-scale gross nitrification rate (GNR) for a temperate forest from 2014 to 2017 in northeastern China. The annual GNR ranged from 71 to 120 kg N ha-1 yr-1 (average 94 ± 10 kg N ha-1 yr-1) over the 4 years in this forest. This result and high stream NO3- loss (4.2-8.9 kg N ha-1 yr-1) suggest that the forested catchment may have been N-saturated. At the catchment scale, the total N output of 10.7 kg N ha-1 yr-1, via leaching and gaseous losses, accounts for 56% of the N input from bulk precipitation (19.2 kg N ha-1 yr-1). This result indicates that the forested catchment is still retaining a large fraction of N from atmospheric deposition. Our study suggests that estimating in situ catchment-scale GNR over several years when combined with other conventional flux estimates can facilitate the understanding of N biogeochemical cycling and changes in the ecosystem N status.

Silicon nanocrystals (SiNCs) with bright bandgap photoluminescence (PL) are of current interest for a range of potential applications, from solar windows to biomedical contrast agents. Here, we use the liquid precursor cyclohexasilane (Si

Peatlands store one third of global soil carbon (C) and up to 15% of global soil nitrogen (N) but often have low plant nutrient availability owing to slow organic matter decomposition under acidic and waterlogged conditions. In rainwater-fed ombrotrophic peatlands, elevated atmospheric N deposition has increased N availability with potential consequences to ecosystem nutrient cycling. Here, we studied how 14 years of continuous N addition with either nitrate or ammonium had affected ericoid mycorrhizal (ERM) shrubs at Whim Bog, Scotland. We examined whether enrichment has influenced foliar nutrient stoichiometry and assessed using N stable isotopes whether potential changes in plant nutrient constraints are linked with plant N uptake through ERM fungi versus direct plant uptake. High doses of ammonium alleviated N deficiency in Calluna vulgaris and Erica tetralix, whereas low doses of ammonium and nitrate improved plant phosphorus (P) nutrition, indicated by the lowered foliar N:P ratios. Root acid phosphatase activities correlated positively with foliar N:P ratios, suggesting enhanced P uptake as a result of improved N nutrition. Elevated foliar delta N-15 of fertilized shrubs suggested that ERM fungi were less important for N supply with N fertilization. Increases in N availability in peat porewater and in direct nonmycorrhizal N uptake likely have reduced plant nitrogen uptake via mycorrhizal pathways. As the mycorrhizal N uptake correlates with the reciprocal C supply from host plants to the soil, such reduction in ERM activity may affect peat microbial communities and even accelerate C loss via decreased ERM activity and enhanced saprotrophic activity. Our results thus introduce a previously unrecognized mechanism for how anthropogenic N pollution may affect nutrient and carbon cycling within peatland ecosystems. (C) 2021 The Authors. Published by Elsevier B.V.

The synthesis and photophysics (UV-vis absorption, emission, and transient absorption) of four neutral heteroleptic cyclometalated iridium(III) complexes (Ir-1-Ir-4) incorporating thiophene/selenophene-diketopyrrolopyrrole (DPP)-substituted N-heterocyclic carbene (NHC) ancillary ligands are reported. The effects of thiophene versus selenophene substitution on DPP and bis- versus monoiridium(III) complexation on the photophysics of these complexes were systematically investigated via spectroscopic techniques and density functional theory calculations. All complexes exhibited strong vibronically resolved absorption in the regions of 500-700 nm and fluorescence at 600-770 nm, and both are predominantly originated from the DPP-NHC ligand. Complexation induced a pronounced red shift of this low-energy absorption band and the fluorescence band with respect to their corresponding ligands due to the improved planarity and extended π-conjugation in the DPP-NHC ligand. Replacing the thiophene units by selenophenes and/or biscomplexation led to the red-shifted absorption and fluorescence spectra, accompanied by the reduced fluorescence lifetime and quantum yield and enhanced population of the triplet excited states, as reflected by the stronger triplet excited-state absorption and singlet oxygen generation.

We provide a case-study for thermal grafting of benzenediazonium bromide onto a hydrogenated Si(111) surface using ab initio molecular dynamics (AIMD) calculations. A sequence of reaction steps is identified in the AIMD trajectory, including the loss of N2 from the diazonium salt, proton transfer from the surface to the bromide ion that eliminates HBr, and deposition of the phenyl group onto the surface. We next assess the influence of the phenyl groups on photophysics of hydrogen-terminated Si(111) slabs. The nonadiabatic couplings necessary for a description of the excited-state dynamics are calculated by combining ab initio electronic structures and reduced density matrix formalism with Redfield theory. The phenyl-terminated slab shows reduced nonradiative relaxation and recombination rates of hot charge carriers in comparison with the hydrogen-terminated slab. Altogether, our results provide atomistic insights revealing that (i) the diazonium salt thermally decomposes at the surface allowing the formation of covalently bonded phenyl group, and (ii) the coverage of phenyl groups on the surface slows down charge carrier cooling driven by electron-phonon interactions, which increases photoluminescence efficiency at the near-infrared spectral region.

The synthesis, crystal structure, and photophysics of a series of neutral cyclometalated iridium(III) complexes bearing substituted N-heterocyclic carbene (NHC) ancillary ligands ((C∧N)2Ir(R-NHC), where C∧N and NHC refer to the cyclometalating ligand benzo[h]quinoline and 1-phenylbenzimidazole, respectively) are reported. The NHC ligands were substituted with electron-withdrawing or -donating groups on C4' of the phenyl ring (R = NO2 (Ir1), CN (Ir2), H (Ir3), OCH3 (Ir4), N(CH3)2 (Ir5)) or C5 of the benzimidazole ring (R = NO2 (Ir6), N(CH3)2 (Ir7)). The configuration of Ir1 was confirmed by a single-crystal X-ray diffraction analysis. The ground- and excited-state properties of Ir1-Ir7 were investigated by both spectroscopic methods and time-dependent density functional theory (TDDFT) calculations. All complexes possessed moderately strong structureless absorption bands at ca. 440 nm that originated from the C∧N ligand based 1π,π*/1CT (charge transfer)/1d,d transitions and very weak spin-forbidden 3MLCT (metal-to-ligand charge transfer)/3LLCT (ligand-to-ligand charge transfer) transitions beyond 500 nm. Electron-withdrawing substituents caused a slight blue shift of the 1π,π*/1CT/1d,d band, while electron-donating substituents induced a red shift of this band in comparison to the unsubstituted complex Ir3. Except for the weakly emissive nitro-substituted complexes Ir1 and Ir6 that had much shorter lifetimes (≤160 ns), the other complexes are highly emissive in organic solutions with microsecond lifetimes at ca. 540-550 nm at room temperature, with the emitting states being predominantly assigned to 3π,π*/3MLCT states. Although the effect of the substituents on the emission energy was insignificant, the effects on the emission quantum yields and lifetimes were drastic. All complexes also exhibited broad triplet excited-state absorption at 460-700 nm with similar spectral features, indicating the similar parentage of the lowest triplet excited states. The highly emissive Ir2 was used as a dopant for organic light-emitting diode (OLED) fabrication. The device displayed a yellow emission with a maximum current efficiency (ηc) of 71.29 cd A-1, a maximum luminance (Lmax) of 32747 cd m-2, and a maximum external quantum efficiency (EQE) of 20.6%. These results suggest the potential of utilizing this type of neutral Ir(III) complex as an efficient yellow phosphorescent emitter.

Carbon (C) fluxes among different components of plant growth are important to forest ecosystem C cycling and are strongly influenced by species composition and resource availability. Although mycorrhizal fungi are crucial for nutrient acquisition and can receive a large fraction of annual net primary production, most studies do not explicitly include carbon flux to mycorrhizal fungi in ecosystem C budgets. We measured annual production of plant components (foliage, wood, fine roots) and mycorrhizal fungi across temperate forest stands varying in species composition. Production of mycorrhizal fungi was estimated using both mass balance and isotopic techniques. Total plant production varied from about 600 g C m−2 y−1 in nearly pure deciduous broadleaf stands down to about 300 g C m−2 y−1 in conifer-dominated stands. In contrast, the production of mycorrhizal fungi was highest in conifer-dominated stands, varying from less than 25 g C m−2 y−1 in deciduous broadleaf stands to more than 175 g C m−2 y−1 in nearly pure conifer stands. Isotopic data indicated that both tree species composition and ecosystem nitrogen (N) availability influenced rates of fungal production. The large investment in mycorrhizal fungi in low-N, conifer-dominated stands demonstrated that a full accounting of ecosystem carbon fluxes to plant and fungal components may help resolve current discrepancies observed in broadscale forest carbon budgets, especially across forest types.

Identifying the mechanisms that structure niche breadth and overlap between species is important for determining how species interact and assessing their functional role in an ecosystem. Without manipulative experiments, assessing the role of foraging ecology and interspecific competition in structuring diet is challenging. Systems with regular pulses of resources act as a natural experiment to investigate the factors that influence the dietary niches of consumers. We used natural pulses of mast‐fruiting of American beech (Fagus grandifolia) to test whether optimal foraging or competition structure the dietary niche breadth and overlap between two congener rodent species (Peromyscus leucopus and P. maniculatus), both of which are generalist consumers. We reconstructed diets seasonally over a 2‐year period using stable isotope analysis (δ13C, δ15N) of hair and of potential dietary items and measured niche dynamics using standard ellipse area calculated within a Bayesian framework. Changes in niche breadth were generally consistent with predictions of optimal foraging theory, with both species consuming more beechnuts (a high‐quality food resource) and having a narrower niche breadth during masting seasons compared to nonmasting seasons when dietary niches expanded and more fungi (a low‐quality food source) were consumed. In contrast, changes in dietary niche overlap were consistent with competition theory, with higher diet overlap during masting seasons than during nonmasting seasons. Overall, dietary niche dynamics were closely tied to beech masting, underscoring that food availability influences competition. Diet plasticity and niche partitioning between the two Peromyscus species may reflect differences in foraging strategies, thereby reducing competition when food availability is low. Such dietary shifts may have important implications for changes in ecosystem function, including the dispersal of fungal spores., Our study tests the opposing predictions of optimal foraging theory and competition theory for dietary niche breadth and overlap of two closely related and ecologically similar rodent species. We find that the mechanism that structures niche dynamics varies under natural pulses of resource availability with changes in niche breadth consistent with predictions of optimal foraging theory and niche overlap consistent with predictions of competition theory.

Heterojunctions of carbon nanotubes interfaced with silicon and doped with AuCl3 can achieve attractive power conversion efficiencies when operated in the photovoltaic regime; however, the cost and long-term stability of such devices must be improved before they could become commercially viable. Here, we investigate the role of chemical treatment of the carbon nanotube/silicon interface with either SOCl2 or HNO3, prior to AuCl3 doping, on the stability of the photovoltaic devices. We find that while both treatments initially lead to similar device performance, devices treated with HNO3 are significantly more stable. Using X-ray photoemission spectroscopy, we demonstrate that pretreatment with the powerful organic oxidant SOCl2 generates a variety of low-oxidation-state silicon species at the nanotube–silicon interface that are not generated by exposure to HNO3. These species and their evolution over time are implicated in the reduced device stability, highlighting the importance of silicon oxidation state...

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light emitting devices due to optoelectronic properties. Understanding the surface chemistry of these materials is of importance as surface defects can introduce trap-states which reduce their functionality. Here we use Density Functional Theory (DFT) to model surface defects introduced by Pb2+ on a CsPbBr3 NC atomistic model. Two types of defects are studied: (i) an under-coordinated Pb2+ surface atom and (ii) Pb2+ atomic or molecular adsorbents to the NC surface. From the DFT calculations we compute the density of states (DOS) and absorption spectra of the defect models to the pristine fully-passivated NC model. We observe that for the low surface defect regime explored here that neither (i) or (ii) produce trap-states inside of the bandgap and exhibit bright optical absorption for the lowest energy transition. From the models studied, it was found that the Pb2+ atomic absorbent provides broadening of the conduction band edge, which implies chemisorption of Pb2+ to the NC surface. At higher defect densities it would be expected that Pb2+ atomic absorbents would introduce trap-states and degrade the opto-electronic properties of these materials.

To assess how nitrogen (N) availability affected ectomycorrhizal functioning and to test a theoretical model of ectomycorrhizal 15N partitioning, we measured C/N and δ15N in soils and nine fungal taxa in two Swedish N addition experiments. Sporocarp C/N and soil C/N decreased with fertilization, implying that N uptake per unit fungal growth increased. The S horizon was more responsive than the F and H horizons to changes in N addition, with N turnover for these horizons of 24, 57, and 57 y, respectively. Fungal and soil δ15N patterns identified fungal N sources, with N acquisition primarily from the S, F, or H horizon for two, five, and two taxa, respectively. With increasing N availability, sporocarp 15N enrichment increased in five taxa, in agreement with our model of fungal-plant N partitioning. However, it decreased in Lactarius rufus and Russula aeruginea, perhaps indicating shifts towards greater inorganic N uptake in these two taxa. This may relate to the generally lower sensitivity of these taxa to N deposition compared to the Cortinarius and Suillus taxa that fit our model of 15N partitioning.

We compared the δ13C and δ15N of forest material with an extensive sporocarp collection to elucidate the role of litter, wood and soil as fungal carbon and nitrogen sources in Finnish boreal Picea abies-dominated forests. Ectomycorrhizal Hydnum and Cortinarius had higher δ15N than other ectomycorrhizal fungi, suggesting use of 15N-enriched, deeper nitrogen. Russula had lower δ15N than other ectomycorrhizal fungi and resembled some litter decay genera, suggesting use of litter-derived nitrogen. There was little variation in δ15N among other genera of ectomycorrhizal fungi, indicating limited functional diversity in nitrogen use. Saprotrophic Leotia, Gymnopus, Hypholoma, Pholiota, Rhodocollybia and Calocera had δ15N values similar to ectomycorrhizal fungi, indicating overlap in use of older nitrogen from soil or roots or use of newly fixed nitrogen. Genera of litter and wood decay fungi varied up to 6‰ in δ13C and 10‰ in δ15N, suggesting large differences in carbon and nitrogen sources and processing. Similar δ13C between white and brown rot wood decay fungi also suggest that white rot fungi do not use lignin-derived carbon. Together, these δ13C and δ15N patterns of fungi from Finnish boreal forests enhance our knowledge of fungal functional diversity and indicate broad use of litter, wood and soil resources.

Soil carbon models typically scale decomposition linearly with soil carbon (C) concentration, but this linear relationship has not been experimentally verified. Here we investigated the underlying biogeochemical mechanisms controlling the relationships between soil C concentration and decomposition rates. We incubated a soil/sand mixture with increasing amounts of finely ground plant residue in the laboratory at constant temperature and moisture for 63 days. The plant residues were rye (Secale cereale, C/N ratio of 23) and wheat straw (Triticum spp., C/N ratio of 109) at seven soil C concentrations ranging from 0.38 to 2.99%. We measured soil respiration, dissolved organic carbon (DOC) concentrations, microbial biomass, and potential enzyme activities over the course of the incubation. Rye, which had higher N and DOC contents, lost 6 to 8 times more C as CO2 compared to wheat residue. Under rye and wheat amendment, absolute C losses as CO2 (calculated per g dry soil) increased linearly with C concentration while relative C losses as CO2 (expressed as percent of initial C) increased with C concentration following a quadratic function. In low C concentration treatments (0.38–0.79% OC), DOC decreased gradually from day 3 to day 63, microbial C increased towards the end in the rye treatment or decreased only slightly with straw amendment, and microbes invested in general enzymes such as proteases and oxidative enzymes. At increasing C levels, enzyme activity shifted to degrading cellulose after 15 days and degrading microbial necromass (e.g. chitin) after 63 days. At the highest C concentrations (2.99% OC), microbial biomass peaked early in the incubation and remained high in the rye treatment and decreased only slightly in the wheat treatment. While wheat lost C as CO2 constantly at all C concentrations, respiration dynamics in the rye treatment strongly depended on C concentration. Our results indicate that litter quality and C concentration regulate enzyme activities, DOC concentrations, and microbial respiration. The potential for non-linear relationships between soil C concentration and decomposition may need to be considered in soil C models and soil C sequestration management approaches.

Ten biscyclometalated monocationic Ir(III) complexes were synthesized and studied to elucidate the effects of extending π-conjugation of the diimine ligand (N^N = 2,2'-bipyridine in Ir1, 2-(pyridin-2-yl)quinoline in Ir2, 2-(pyridin-2-yl)[6,7]benzoquinoline in Ir3, 2-(pyridin-2-yl)-[7,8]benzoquinoline in Ir4, phenanthroline in Ir5, benzo[ f][1,10]phenanthroline in Ir6, naphtho[2,3- f][1,10]phenanthroline in Ir7, 2,2'-bisquinoline in Ir8, 3,3'-biisoquinoline in Ir9, and 1,1'-biisoquinoline in Ir10) via benzannulation at 2,2'-bipyridine on the excited-state properties and reverse saturable absorption (RSA) of these complexes. Either a bathochromic or a hypsochromic shift of the charge-transfer absorption band and emission spectrum was observed depending on the benzannulation site at the 2,2'-bipyridine ligand. Benzannulation at the 3,4-/3',4'-position or 5,6-/5',6'-position of 2,2'-bipyridine ligand or at the 6,7-position of the quinoline ring on the N^N ligand caused red-shifted charge-transfer absorption band and emission band for complexes Ir2, Ir8, Ir10 vs Ir1 and Ir3 vs Ir2, while benzannulation at the 4,5-/4',5'-position of 2,2'-bipyridine ligand or at the 7,8-position of the quinoline ring on the N^N ligand induced a blue shift of the charge-transfer absorption and emission bands for complex Ir9 vs Ir1 and Ir4 vs Ir2. However, benzannulation at the 2,2',3,3'-position of 2,2'-bipyridine or 5,6-position of phenanthroline ligand had no impact on the energy of the charge-transfer absorption band and emission band of complexes Ir5-Ir7 compared with those of Ir1. The observed phenomenon was explained by the frontier molecular orbital (FMO) symmetry analysis. Site-dependent benzannulation also impacted the spectral feature and intensity of the triplet transient absorption spectra and lifetimes drastically. Consequently, the RSA strength of these complexes varied with a trend of Ir7 > Ir5 ≈ Ir6 ≈ Ir1 > Ir3 > Ir2 > Ir10 > Ir4 > Ir8 > Ir9 at 532 nm for 4.1 ns laser pulses.

The Arctic is experiencing rapid climatic and environmental changes, which could alter diets of nonmigratory herbivores both within and between populations. Here, we used carbon and nitrogen stable isotope analysis (δ13C and δ15N) in hair to infer summer dietary differences of Rangifer tarandus platyrhynchus (nonmigratory reindeer) in Nordenskioldland, Svalbard and used regression models to predict how reindeer dietary intake depend on climatic variables. In linear regression models, current-year and last-year July temperatures positively correlated with both the δ13C and δ15N of reindeer hair, and were stronger predictors of isotopic signatures than July precipitation. δ13C and δ15N analysis indicated robust dietary differences between populations separated by less than 50 km and within these valley systems in the proportions of nonmycorrhizal vascular plants and mosses. Remote sensing (NDVI) and isotopic data together suggested an early-season switch from moss to vascular plant dependence in valleys closer to the sea, suggesting both high site fidelity and localized differences in forage availability related to the onset of the growing season. 13C photosynthetic discrimination increased with the rising atmospheric pCO2, indicating that Svalbard plants are already responding physiologically to rising CO2 concentrations. Calves were higher in δ13C and δ15N than adults, consistent with a weak trophic effect. We also determined how hair C:N correlated with δ13C and δ15N patterns. Overall, these data provide evidence that δ13C and δ15N measurements can detect dietary shifts over short time periods and fine spatial scales, indicating that isotopic studies can help monitor herbivory in the changing Arctic.

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light-emitting devices due to optoelectronic properties that can be tuned/optimized via halide composition, surface passivation, doping, and confinement. Compared to bulk materials, certain excited-state properties in NCs can be adjusted by electronic confinement effects such as suppressed hot carrier cooling and enhanced radiative recombination. Here we use spinor Kohn-Sham orbitals (SKSOs) with spin-orbit coupling (SOC) interaction as a basis to compute excited-state dissipative dynamics simulations on a fully passivated CsPbBr3 NC atomistic model. Redfield theory in the density matrix formalism is used to describe electron-phonon interactions which drive hot carrier cooling and nonradiative recombination ( knonrad). Radiative recombination ( krad) is calculated through oscillator strengths using SKSO basis. From krad and krad + knonrad, we compute a theoretical photoluminescence quantum yield (PLQY) of 53%. Computed rates of hot carrier cooling ( kcooling ≈ 10-1 1/ps) compare favorably with what has been reported in the literature. Interestingly, we observe that hot electron cooling slows down near the band edge, which we attribute to large SOC in the conduction band combined with strong confinement, which creates subgaps above the band edge. This slow carrier cooling could potentially impact hot carrier extraction before complete thermalization in photovoltaics (PVs). Implications of this work suggest that strong/intermediate confined APbX3 NCs are better suited to applications in PVs due to slower carrier cooling near the conduction band edge, while intermediate/weak confined NCs are more appropriate for light-emitting applications, such as LEDs.

Silicon nanowires (SiNWs) exhibit unique optoelectronic properties originating from one-dimensional confinement effect. Technologically relevant properties—including band gap, radiative and nonradi...

Humans have dramatically increased atmospheric nitrogen (N) deposition globally. At the coarsest resolution, N deposition is correlated with shifts from ectomycorrhizal (EcM) to arbuscular mycorrhizal (AM) tree dominance. At finer resolution, ectomycorrhizal fungal (EcMF) and arbuscular mycorrhizal fungal (AMF) communities respond strongly to long-term N deposition with the disappearance of key taxa. Conifer-associated EcMF are more sensitive than other EcMF, with current estimates of critical loads at 5–6 kg ha−1 yr−1 for the former and 10–20 kg ha−1 yr−1 for the latter. Where loads are exceeded, strong plant-soil and microbe-soil feedbacks may slow recovery rates after abatement of N deposition. Critical loads for AMF and tropical EcMF require additional study. In general, the responses of EcMF to N deposition are better understood than those of AMF because of methodological tractability. Functional consequences of EcMF community change are linked to decreases by fungi with medium-distance exploration strategies, hydrophobic walls, proteolytic capacity, and perhaps peroxidases for acquiring N from soil organic matter. These functional losses may contribute to declines in forest floor decomposition under N deposition. For AMF, limited capacity to directly access complexed organic N may reduce functional consequences, but research is needed to test this hypothesis. Mycorrhizal biomass often declines with N deposition, but the relative contributions of alternate mechanisms for this decline (lower C supply, higher C cost, physiological stress by N) have not been quantified. Furthermore, fungal biomass and functional responses to N inputs probably depend on ecosystem P status, yet how N deposition-induced P limitation interacts with belowground C flux and mycorrhizal community structure and function is still unclear. Current ‘omic analyses indicate potential functional differences among fungal lineages and should be integrated with studies of physiology, host nutrition, growth and health, fungal and plant community structure, and ecosystem processes. Forest mycorrhizal fungal community composition responds strongly to N deposition across broad ranges of spatial, temporal and phylogenetic scales, with functional consequences—including altered tree nutrition and C, N, and P cycling—that are substantial but only partially understood.

We performed x-ray photoelectron spectroscopy measurements on a thin film of Si nanocrystals (SiNCs) while applying DC or AC external biases to extract the resistance and the capacitance of the thin film. The measurement consists of the application of 10 V DC or square wave pulses of 10 V amplitude to the sample at various frequencies ranging from 0.01 to 1 MHz while recording x-ray photoemission data. To analyze the data, we propose three different models with varying degrees of accuracy. The calculated capacitance of SiNCs agrees with the experimental value in the literature.

The effects of nitrogen (N) deposition on forests largely depend on its fate after entering the ecosystem. While several studies have addressed the forest fate of N deposition using 15 N tracers, the long-term fate and redistribution of deposited N in tropical forests remains unknown. Here, we applied 15 N tracers to examine the fates of deposited ammonium (NH4 + ) and nitrate (NO3 - ) separately over three years in a primary and a secondary tropical montane forest in southern China. Three months after 15 N tracer addition, over 60% of 15 N was retained in the studied forests. Total ecosystem retention did not change over the study period, but between three months and three years following deposition 15 N recovery in plants increased from 10% to 19% and 13% to 22% in the primary and secondary forest, respectively, while 15 N recovery in the organic soil declined from 16% to 2% and 9% to 2%. Mineral soil retained 50% and 35% of 15 N in the primary and secondary forests, with retention being stable over time. The total ecosystem retention of the two N forms did not differ significantly, but plants retained more 15 NO3 - than 15 NH4 + and the organic soil more 15 NH4 + than 15 NO3 - . Mineral soil did not differ in 15 NH4 + and 15 NO3 - retention. Compared to temperate forests, proportionally more 15 N was distributed to mineral soil and plants in these tropical forests. Overall, our results suggest that atmospherically deposited NH4 + and NO3 - is rapidly lost in the short-term (months) but thereafter securely retained within the ecosystem, with retained N becoming redistributed to plants and mineral soil from the organic soil. This long-term N retention may benefit tropical montane forest growth and enhance ecosystem carbon sequestration.

Studies using carbon isotope differences between C

Summary • Nitrogen isotope (δ 15 N) patterns in plants may provide insight into plant N dynamics. Here, two analytical models of N-isotope cycling in plants and mycorrhizal fungi were tested, as dominant plants in many forest ecosystems obtain most of their N through intereactions with mycorrhizal fungi. • Fungi were treated either as a single well-mixed N pool, or as two N pools (one available, plus one not available, for transfer to the host). Models were compared against complete biomass and 15 N budgets from culture studies of nonmycorrhizal and ectomycorrhizal Pinus sylvestris (colonized with Suillus luteus or Thelephora terrestris ) grown exponentially at low and high N supply. • Fungal biomass and N increased at low N relative to high N supply, whereas needle δ 15 N decreased. Needle δ 15 N correlated strongly and negatively with biomass of extraradical hyphae. Our data and models suggest that low plant δ 15 N values in low productivity and N-limited environments result partly from high retention of 15 N-enriched N by mycorrhizal fungi; this retention was driven by increased C flux to fungi under N-limited conditions. The two-pool model of fungal N accounted for greater variability in plant δ 15 N than the one-pool model. • Plant δ 15 N patterns may indicate relative allocation of fixed C from plants to mycorrhizal fungi under some conditions. Studies are needed on whether patterns observed in culture can be applied to interpret field measurements of δ 15N.

SummaryRecently, several saprotrophic genera have been found to invade/interact with plant roots in laboratory growth experiments, and this coincides with reports of abundant saprotrophic fungal sequences in plant roots. However, it is uncertain if this reflects field phenomena, and if reports on coincidentally amplified saprotrophs are simply coincidental.We investigated root invasion by presumed saprotrophic fungi by focusing on the large genus Mycena in 1) a systematic analysis of the occurrence of saprotrophic fungi in new and previously published ITS1/ITS2 datasets generated from roots of 10 mycorrhizal plant species, and 2) we analysed natural abundances of 13C/15N stable isotope signatures of fungal/plant communities from five comparable field locations to examine the trophic status of Mycena species.Mycena was the only saprotrophic genus consistently found in 9 of 10 plant host roots, with high within-host variation in Mycena sequence proportions (0-80%) recovered. Mycena carpophores displayed isotopic signatures consistent with published 13C/15N profiles of both saprotrophic or mutualistic lifestyles, with considerable intraspecific variation, resembling the patterns seen in growth experiments. These results indicate that multiple Mycena species opportunistically invade the roots of a range of plant species, possibly forming a spectrum of interactions. This potentially challenges our general understanding of fungal ecology.Originality significance statementThis is the first study to apply a dual approach of systematic metabarcoding of plant roots and stable isotope signatures on dried field material to the large and common saprotrophic fungal genus Mycena. This is significant as it shows that members of this genus, normally not expected to be found inside plant roots at all, are in fact associated eith multiple plant hosts. The study furthermore shows that species in this genus may occupy different ecological roles in the field besides being saprotrophic. That a large and common fungal genus known to be a quantitatively important litter decayer can be an opportunistic root invader and interact with host plants is of interest to all mycologists and ecologists working on plant-fungus/microb symbiosis.

Using a combination of density-gradient and analytical ultracentrifugation, we studied the photophysical profile of CsPbBr

Stable soil pH is a key property in maintaining an ecosystem's structure, function, and sustainability. Increasing atmospheric deposition and grassland use on the Tibetan Plateau (TP) may increase the soil acidification risk, but we lack such information to date. Here, we evaluated the soil acidification risk in the TP, by comparing it with that in the Mongolia Plateau (MP) and applying the acid–base balance principles on atmospheric inputs, soils, and plants from 1980 to 2019. Cumulative acid input was lower in the TP than in the MP. Sulfur contributed more to acidity than nitrogen and atmospheric deposition contributed more to acidity than grassland use. Acid input was mainly influenced by local industry, animal husbandry and transportation in the MP, while in the TP it was also affected by the long-distance transportation of pollutants from South Asia and southern China. Overall, the TP was less acid-sensitive than the MP because of higher inorganic carbon content. However, soils in the southeastern TP, covering 21% of the total area, were acid-sensitive due to low levels of soil exchangeable base cation (EBCs) and lack of calcium carbonate. Coincidentally, the southeastern region has the highest concentration of acid input in the TP due to more rapid development and stronger influence of adjacent high acid deposition regions than others. Therefore, the acidification risk to the southeastern region is much higher than to other regions of the TP and the MP; in this region, the EBCs are likely to be depleted approximately 95 years earlier than in the MP. The findings of this study provide insights into the response of the TP to global change. For the ecosystem sustainability of southeastern TP, control of atmospheric acid deposition, especially sulfur deposition, in both local and adjacent regions and nations is required.

Conifers are considered to prefer to take up ammonium (NH4 + ) over nitrate (NO3 - ). However, this conclusion is mainly based on hydroponic experiments that separate roots from soils. It remains unclear to what extent mature conifers can use nitrate compared to ammonium under field conditions where both roots and soil microbes compete for nitrogen (N). We conducted an in situ whole mature tree nitrogen-15 (15 N) labeling experiment (15 NH4 + vs 15 NO3 - ) over 15 d to quantify ammonium and nitrate uptake and assimilation rates in four 40-yr-old monoculture coniferous plantations (Pinus koraiensis, Pinus sylvestris, Picea koraiensis and Larix olgensis, respectively). For the whole tree, 15 NO3 - contributed 39% to 90% to total 15 N tracer uptake among four plantations during the study period. At day 3, the 15 NO3 - accounted for 77%, 64%, 62% and 59% by Larix olgensis, Pinus koraiensis, Pinus sylvestris and Picea koraiensis, respectively. Our study indicates that mature coniferous trees assimilated nitrate as efficiently as ammonium from soils even at low soil nitrate concentration, in contrast to the results from hydroponic experiments showing that ammonium uptake dominated over nitrate. This implies that mature conifers can adapt to increasing availability of nitrate in soil, for example, under the context of globalization of N deposition and global warming.

The biological conversion of frozen carbon-rich soil (permafrost) into greenhouse gases such as carbon dioxide could cause a positive feedback to climate change. Another significant consequence of permafrost thaw is the collapse of soil structure and subsequent higher water table that can shift vegetation toward water-adapted plant communities that emit high concentrations of methane (CH4). Plants and microbes respond rapidly to labile carbon (C) and nitrogen (N) released from permafrost thaw, however, the microbial response to phosphorus (P) is unknown. Here we investigated how the nutrient status of permafrost and peat affect microbial activities in four minerotrophic communities in a peatland undergoing permafrost thaw. We experimentally fertilized soils in vitro with a permafrost soil slurry, inorganic P, organic N, or organic N and P. This method isolated the effect of permafrost thaw on microbial processes by removing the confounding effect of plant-soil interactions. The four peatland communities include 1. palsas (intact permafrost mounds rising above the surrounding peatlands), 2. pockets of collapsed palsas dominated by Sphagnum fuscum, 3. adjacent eutrophic Sphagnum-dominated lawns with thawing permafrost and 4. inundated, sedge-dominated minerotrophic fens with no permafrost remaining. Permafrost had high extractable inorganic N concentrations, averaging 30 µg N g-1 soil dry weight (dw), whereas extractable P concentrations were low, averaging 1.4 µg P g-1 soil dw. While N concentrations in the permafrost were over four times the concentration in adjacent peatland communities, extractable P concentrations were relatively lower. Sphagnum lawns positioned at the base of palsas, had nine times the extractable P concentrations averaging 12.6 µg P g-1 soil dw compared to the permafrost, suggesting that P availability increases as permafrost thaws. However, in the fen where no permafrost remains, extractable P concentrations were again low, 2.4 µg P g-1 soil dw, despite high total P. These fen communities are also marked by higher iron concentrations, likely resulting in P immobilization by higher concentrations of metals. The addition of inorganic P and the combination of organic N and P in these fen sites strongly enhanced CH4 oxidation rates while organic N did not, indicating the importance of P for these energy intensive transformations. Nutrient amendments did not have a significant effect on CH4 production rates, however, permafrost slurries significantly decreased CH4 production in Sphagnum lawn communities, suggesting an unknown inhibitory effect of permafrost chemistry on CH4 production. The results of our study highlight the effects of permafrost degradation on nutrient release and provide new insight into how nutrients unlocked from permafrost affects greenhouse gases.

Nitrification is a crucial step in ecosystem nitrogen (N) cycling, but scaling up from plot-based measurements of gross nitrification to catchments is difficult. Here, we employed a newly developed method in which the oxygen isotope anomaly (Δ

Determining appropriate farming management practices to adapt to climate change with lower environmental costs is important for sustainable agricultural production. In this study, a long-term experiment (1985–2019) was conducted under different management practices combining fertilization rate (no, low and high N fertilizer, N0, N1 and N2), straw additions (no, low and high addition, S0, S1 and S2) with conservation tillage (no-tillage, NT) in the North China Plain (NCP). The Denitrification-Decomposition (DNDC) model was firstly evaluated using the experimental data, and then applied to simulate the changes of crop yields, soil organic carbon (SOC), and N2O emissions under different management practices combined with climate change scenarios, under low and high emission scenarios of societal development pathways (SSP245 and SSP585, respectively) with climate projections from 2031 to 2100. Under the low emission scenario (SSP245), wheat yields were the highest with the NT-N1-S2 treatment (a 23% increase relative to the baseline (1981–2010)). For maize yields, the NT-N1-S1 treatment increased 46% relative to baseline under the SSP585, whereas, the yields increased less in all treatments under SSP245–2040s. The SOC was predicted to increase by 6–60% by 2100 under SSP245. Straw addition and tillage were the main factors influencing SOC. N fertilizer was the most important driver for wheat and maize yields, however, N2O emissions from soil increased with increased application of N fertilizer. Therefore, the no-tillage method under low N fertilizer and high straw addition (NT-N1-S2) is recommended to promote crop yields and substantially increase SOC under SSP245 and SSP585. Conservation agriculture practices can potentially offset crop yield reductions, increase soil quality, and reduce greenhouse gas emissions in the NCP, and ensure crop production to meet the growing demand for food under future climate change.