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Background and aims: The amount of nitrogen (N) derived from symbiotic N2 fixation by legumes in grasslands might be affected by anthropogenic N and phosphorus (P) inputs, but the underlying mechanisms are not known. Methods: We evaluated symbiotic N2 fixation in 17 natural and semi-natural grasslands on four continents that are subjected to the same full-factorial N and P addition experiment, using the 15N natural abundance method. Results: N as well as combined N and P (NP) addition reduced aboveground legume biomass by 65% and 45%, respectively, compared to the control, whereas P addition had no significant impact. Addition of N and/or P had no significant effect on the symbiotic N2 fixation per unit legume biomass. In consequence, the amount of N fixed annually per grassland area was less than half in the N addition treatments compared to control and P addition, irrespective of whether the dominant legumes were annuals or perennials. Conclusion: Our results reveal that N addition mainly impacts symbiotic N2 fixation via reduced biomass of legumes rather than changes in N2 fixation per unit legume biomass. The results show that soil N enrichment by anthropogenic activities significantly reduces N2 fixation in grasslands, and these effects cannot be reversed by additional P amendment. [ABSTRACT FROM AUTHOR]

Grassland ecosystems support large communities of aboveground herbivores that are known to directly and indirectly affect belowground properties such as the microbial community composition, richness, or biomass. Even though multiple species of functionally different herbivores coexist in grassland ecosystems, most studies have only considered the impact of a single group, i.e., large ungulates (mostly domestic livestock) on microbial communities. Thus, we investigated how the exclusion of four groups of functionally different herbivores affects bacterial community composition, richness, and biomass in two vegetation types with different grazing histories. We progressively excluded large, medium, and small mammals as well as invertebrate herbivores using exclosures at 18 subalpine grassland sites (9 per vegetation type). We assessed the bacterial community composition using terminal restriction fragment length polymorphism (T-RFLP) at each site and exclosure type during three consecutive growing seasons (2009-2011) for rhizosphere and mineral soil separately. In addition, we determined microbial biomass carbon (MBC), root biomass, plant carbon:nitrogen ratio, soil temperature, and soil moisture. Even though several of these variables were affected by herbivore exclusion and vegetation type, against our expectations, bacterial community composition, richness, or MBC were not. Yet, bacterial communities strongly differed between the three growing seasons as well as to some extent between our study sites. Thus, our study indicates that the spatiotemporal variability in soil microclimate has much stronger effects on the soil bacterial communities than the grazing regime or the composition of the vegetation in this high-elevation ecosystem. [ABSTRACT FROM AUTHOR]

Background & aims: Herbivore-driven changes to soil properties can influence the decomposition rate of organic material and therefore soil carbon cycling within grassland ecosystems. We investigated how aboveground foraging mammalian and invertebrate herbivores affect mineral soil decomposition rates and associated soil properties in two subalpine vegetation types (short-grass and tall-grass) with different grazing histories. Methods: Using exclosures with differing mesh sizes, we progressively excluded large, medium and small mammals and invertebrates from the two vegetation types in the Swiss National Park (SNP). Mineral soil decomposition rates were assessed using the cotton cloth (standard substrate) method between May and September 2010. Results: Decomposition displayed strong spatio-temporal variability, best explained by soil temperature. Exclusion of large mammals increased decomposition rates, but further exclusion reduced decomposition rates again in the lightly grazed (tall-grass) vegetation. No difference among treatments was found in the heavily grazed (short-grass) vegetation. Heavily grazed areas had higher decomposition rates than the lightly grazed areas because of higher soil temperatures. Microbial biomass carbon and soil C:N ratio were also linked to spatio-temporal decomposition patterns, but not to grazing history. Conclusions: Despite altering some of the environmental controls of decomposition, cellulose decomposition rates in the SNP's subalpine grasslands appear to be mostly resistant to short-term herbivore exclusion. [ABSTRACT FROM AUTHOR]

Grasslands support large populations of herbivores and store up to 30% of the world's soil carbon (C). Thus, herbivores likely play an important role in the global C cycle. However, most studies on how herbivory impacts the largest source of C released from grassland soils-soil carbon dioxide (CO) emissions-only considered the role of large ungulates. This ignores all other vertebrate and invertebrate herbivores and their collective effects on ecosystem properties. We progressively excluded large, medium, and small vertebrates and invertebrates from two subalpine grasslands (productive, heavily grazed short-grass; less productive, lightly grazed tall-grass) using size-selective fences, assessed the impact on soil CO emissions and related biotic and abiotic variables. Exclusion resulted in significant changes in soil CO emissions in both vegetation types. Short-grass soil CO emissions progressively increased when large and medium mammals were excluded. However, no difference was detected among plots were all or no herbivores grazed. In contrast, tall-grass soil CO emissions were not affected by mammal exclusion, but excluding all herbivores lead to reduced emissions. Soil micro-climatic parameters best predicted the patterns of soil CO emissions in short-grass vegetation, whereas root biomass was the best predictor of CO release in tall-grass vegetation. Our results showed that diverse herbivore communities affect soil respiration differently than assumed from previous studies that only excluded large ungulates. Such information is important if we are to understand how changes in herbivore species composition-as could happen through altered management practices, extinction or invasion-impact grassland C storage and release. [ABSTRACT FROM AUTHOR]

Our understanding of carbon (C) dynamics within savannas is very limited, especially how source/sink dynamics are influenced by the resident biota. Previous measurements of epigeal termite mounds (termitaria), ubiquitous in many savannas, have shown that they are considerable point sources of soil carbon dioxide (CO), whereas CO measurements collected outside the mounds were generally assumed to be independent of termite activity. However, no measurements were conducted along gradients away from the mounds to confirm this. We quantified daytime soil CO emissions (soil respiration) along gradients from the center to 20 m from the mound edge in Serengeti National Park, and measured soil temperature/moisture, macro-invertebrate abundance, and vegetation height as variables potentially influencing these emissions. Further, we quantified how far into the savanna termitaria impact CO emissions. As in other studies, we found the highest soil CO fluxes at the termitaria-center and considerably lower fluxes in the surrounding savanna. Macro-invertebrate abundance was associated with the differences in emissions measured, whereas the other variables were not. The analysis of spatial autocorrelation revealed significantly lower fluxes between the termitaria edge and up to 9 m from the edge compared to the values measured at the termitaria-center and between 10 and 20 m from the termitaria edge. When extrapolating the emissions across the landscape our results suggest that the lower CO emissions found between the edge and 9 m fully compensate for the high fluxes measured at the termitaria center. Consequently, our findings provide evidence that termitaria might influence the savanna C source-sink dynamics differently than previously thought. [ABSTRACT FROM AUTHOR]

Interest in soil C storage and release has increased in recent years. In addition to factors such as climate/land-use change, vertebrate animals can have a considerable impact on soil CO emissions. To date, most research has considered herbivores, while the impact of omnivorous animals has rarely been investigated. Our goal was to determine how European wild boars ( Sus scrofa L.), large omnivores that consume soil-inhabiting animals and belowground plant parts by grubbing in the soil, affect soil C dynamics. We measured soil respiration (CO), temperature, and moisture on paired grubbed and non-grubbed plots in six hardwood forest stands for a 3-year period and sampled fine root and microbial biomass at the beginning and after 2 years of the study. We also measured the percentage of freshly disturbed forest soil within the larger surroundings of each stand and used this information together with hunting statistics and forest cover data to model the total amount of CO released from Swiss forest soils due to grubbing during 1 year. Soil CO emissions were significantly higher on grubbed compared to non-grubbed plots during the study. On average 23.1% more CO was released from these plots, which we associated with potential alterations in CO diffusion rates, incorporation of litter into the mineral soil and higher fine root/microbial biomass. Thus, wild boars considerably increased the small-scale heterogeneity of soil properties. Roughly 1% of Switzerland's surface area is similar to our sites (boar density/forest cover). Given the range of forest soil disturbance of 27-54% at our sites, the geographic information system model predicted that boar grubbing would lead to the release of an additional 49,731.10-98,454.74 t CO year. These values are relatively small compared to total soil emissions estimated for Swiss hardwood forests and suggest that boars will have little effect on large-scale emissions unless their numbers increase and their range expands dramatically. [ABSTRACT FROM AUTHOR]

We examined the role of red deer ( Cervus elaphus L.) in translocating phosphorus (P) from their preferred grazing sites (short-grass vegetation on subalpine grasslands) to their wider home range in a subalpine grassland ecosystem in the Central European Alps. Phosphorus was used because it is the limiting nutrient in these grasslands. When we compared P removal of aboveground biomass due to grazing with P input due to the deposit of feces on a grid of 268 cells (20 m × 20 m) covering the entire grassland, we detected distinct spatial patterns: the proportion of heavily grazed short-grass vegetation increased with increasing soil-P pool, suggesting that red deer preferably grazed on grid cells with a higher soil-P pool. Biomass consumption related to increased proportion of short-grass vegetation, and therefore P removal, increased with increasing soil-P pool. However, within the two vegetation types (short-grass and tall-grass), consumption was independent from soil-P pool. In addition, P input rates from defecation increased with increasing soil-P pool, resulting in a constant mean net P loss of 0.083 kg ha−1 y−1 (0.03%–0.07% of soil-P pool) independent of both soil-P pool and vegetation type. Thus, there was no P translocation between grid cells with different soil-P pools or between short-grass and tall-grass vegetation. Based on these results, it is likely that the net rate of P loss is too small to explain the observed changes in vegetation composition from tall-herb/meadow communities to short-grass and from tall-grass to short-grass on the grassland since 1917. Instead, we suggest that the grazing patterns of red deer directly induced succession from tall-herb/meadow communities to short-grass vegetation. Yet, it is also possible that long-term net soil-P losses indirectly drive plant succession from short-grass to tall-grass vegetation, because nutrient depletion could reduce grazing pressure in short-grass vegetation and enable the characteristic tall-grass species Carex sempervirens Vill. to establish. [ABSTRACT FROM AUTHOR]

Despite the formal exponential decay behavior of Wannier functions (WFs), their spatial extent, which is a key parameter determining the computational cost of local correlation calculations for solids, is still rather large. The problems with the localization of the WFs can partly be attributed to their mutual orthogonality. Possibilities of reduction of the spatial extent of the WFs without losing the accuracy of the calculations are investigated. A method for generation of nonorthogonal ultralocalized functions based on maximization of their Löwdin populations is developed. A scheme for fitting of the WFs and nonorthogonal localized functions with a limited support is proposed. The calculations show that by combining both techniques one can obtain quite compact linearly independent localized functions, which may significantly decrease the computational cost in post-HF calculations. [ABSTRACT FROM AUTHOR]

In many mountain regions, traditional agriculture and forestry are no longer economically viable and less intense land-use is becoming more and more widespread. Thus, the importance of understanding secondary succession in these abandoned systems increases. This study is based on a comparison of historic (1957) and present tree data (2001) from subalpine forest stands located in the Swiss National Park (SNP), where all management was stopped in 1914. The two data sets contain information on tree and sapling density as well as diameter distribution for all tree species present. Using time-series analyses, space for time substitution and multivariate methods (PCoA, minimum spanning tree analysis), we investigated if successional changes can be detected within the forest stands in the SNP. Our results showed that the stands studied are developing from a stage dominated by mountain pine (Pinus montana Miller) to a late successional stage dominated by Swiss stone pine (Pinus cembra L.) and European larch (Larix decidua Miller). This shift in species composition, which was observed in both the tree and sapling layer, was accompanied by a significant decrease in tree density (stems/ha). We also found that stand disturbances, such as fungal diseases, parasitic insects, ungulate browsing, windthrow or snow pressure, have not prevented succession from mountain pine to Swiss stone pine-larch communities. The minimum spanning tree analysis revealed that the sixteen observed 44-year-time-series cover at least 110 years of succession. This time frame is the shortest possible duration for a successional development starting from a 95 to 125-year-old mountain pine stand. The successional changes depicted in our study indicate how similar areas in the Central European Alps might develop in the near future when management ceases. [ABSTRACT FROM AUTHOR]

The full capacity of contemporary parallel computers can, in the context of iterative ab initio procedures like, for example, self-consistent field (SCF) and multiconfigurational SCF, only be utilized if the disk and input/output (I/O) capacity are fully exploited before the implementation turns to an integral direct strategy. In a recent report on parallel semidirect SCF http://www.tc.cornell.edu/er/media/1996/collabrate.html, http://www.fp.mcs.anl.gd/grand-challenges/chem/nondirect/index.html it was demonstrated that super-linear speedups are achievable for algorithms that exploit scalable parallel I/O. In the I/O-intensive SCF iterations of this implementation a static load balancing, however, was employed, dictated by the initial iteration in which integral evaluation dominates the central processing unit activity and thus determines the load balancing. In the present paper we present the first implementation in which load balancing is achieved throughout the whole SCF procedure, i.e. also in subsequent iterations. The improved scalability of our new algorithm is demonstrated in some test calculations, for example, for 63-node calculation a speedup of 104 was observed in the computation of the two-electron integral contribution to the Fock matrix. [ABSTRACT FROM AUTHOR]

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The metalation of bis(diphenylphosphanyl)amine, HN(PPh2)2 ( 5), with RbO tBu in the presence of N,N,N′,N′′,N′′-pentamethyldiethylenetriamine ( PMDTA ( 3)) in toluene surprisingly affords the nearly PMDTA free RbN(PPh2)2 ( 6a). Recrystallization of 6a from tetrahydrofuran ( THF) yields RbN(PPh2)2ċ0.5 THF ( 6b). Compounds 6a, b crystallize in thin needles; however, these are not suitable for X-ray structure analyses. The reactions of 5 with MO tBu ( M=Rb, Cs) in the presence of 18-crown-6 in toluene yield the monomeric, pale yellow rubidium and caesium complexes [Rb(18-crown-6)(N(PPh2)2)] ( 7) and [Cs(18-crown-6)(N(PPh2)2)] ( 8), respectively. Allowing to stand a solution of 8 in THF for three months at 20°C results in a cleavage product of 8. This is identified as the dimeric yellow complex [(Cs(18-crown-6))2(μ-N*P(H)Ph2)2]ċ THF ( 9). The source of the hydrogen atom in the bridging phosphorane iminate anion [N*P(H)Ph2]− is uncertain. Compounds 7– 9 are structurally characterized by X-ray analyses. These reveal that [N(PPh2)2]− acts as P-ligating chelate in 7, whereas it coordinates the Cs+ as N-donor as well as η2 C-donor with one phenyl group in 8. No phosphorus coordination is observed in 8. The two caesium cations in 9 are two-fold N-bridged by [N*P(H)Ph2]−. The coordination sphere of each caesium atom is completed by a 18-crown-6 ligand. The solid state 13C NMR spectrum of 8 reveals dynamic phenomena (rotation of the 18-crown-6 ligand). In the solid state 31P spectrum of 8, 31P, 31P– J-coupling is observed between the chemically non-equivalent phosphorus sites ( J=390 Hz). [ABSTRACT FROM AUTHOR]

Ecological models predict that the effects of mammalian herbivore exclusion on plant diversity depend on resource availability and plant exposure to ungulate grazing over evolutionary time. Using an experiment replicated in 57 grasslands on six continents, with contrasting evolutionary history of grazing, we tested how resources (mean annual precipitation and soil nutrients) determine herbivore exclusion effects on plant diversity, richness and evenness. Here we show that at sites with a long history of ungulate grazing, herbivore exclusion reduced plant diversity by reducing both richness and evenness and the responses of richness and diversity to herbivore exclusion decreased with mean annual precipitation. At sites with a short history of grazing, the effects of herbivore exclusion were not related to precipitation but differed for native and exotic plant richness. Thus, plant species' evolutionary history of grazing continues to shape the response of the world's grasslands to changing mammalian herbivory., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Herbivores alter plant biodiversity (species richness) in many of the world's ecosystems, but the magnitude and the direction of herbivore effects on biodiversity vary widely within and among ecosystems. One current theory predicts that herbivores enhance plant biodiversity at high productivity but have the opposite effect at low productivity. Yet, empirical support for the importance of site productivity as a mediator of these herbivore impacts is equivocal. Here, we synthesize data from 252 large-herbivore exclusion studies, spanning a 20-fold range in site productivity, to test an alternative hypothesis-that herbivore-induced changes in the competitive environment determine the response of plant biodiversity to herbivory irrespective of productivity. Under this hypothesis, when herbivores reduce the abundance (biomass, cover) of dominant species (for example, because the dominant plant is palatable), additional resources become available to support new species, thereby increasing biodiversity. By contrast, if herbivores promote high dominance by increasing the abundance of herbivory-resistant, unpalatable species, then resource availability for other species decreases reducing biodiversity. We show that herbivore-induced change in dominance, independent of site productivity or precipitation (a proxy for productivity), is the best predictor of herbivore effects on biodiversity in grassland and savannah sites. Given that most herbaceous ecosystems are dominated by one or a few species, altering the competitive environment via herbivores or by other means may be an effective strategy for conserving biodiversity in grasslands and savannahs globally.