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1.
Sci Data ; 11(1): 478, 2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38724554

RESUMO

Soil organic carbon (SOC) is a soil health indicator and understanding dynamics changing SOC stocks will help achieving net zero goals. Here we present four datasets featuring 11,750 data points covering co-located aboveground and below-ground metrics for exploring ecosystem SOC dynamics. Five sites across England with an established land use contrast, grassland and woodland next to each other, were rigorously sampled for aboveground (n = 109), surface (n = 33 soil water release curves), topsoil, and subsoil metrics. Commonly measured soil metrics were analysed in five soil increments for 0-1 metre (n = 4550). Less commonly measured soil metrics which were assumed to change across the soil profile were measured on a subset of samples only (n = 3762). Additionally, we developed a simple method for soil organic matter fractionation using density fractionation which is part of the less common metrics. Finally, soil metrics which may impact SOC dynamics, but with less confidence as to their importance across the soil profile were only measured on topsoil (~5-15 cm = mineral soil) and subsoil (below 50 cm) samples (n = 2567).


Assuntos
Carbono , Pradaria , Solo , Solo/química , Carbono/análise , Inglaterra , Florestas , Ecossistema
2.
Glob Chang Biol ; 30(1): e17086, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38273496

RESUMO

Plant communities are being exposed to changing environmental conditions all around the globe, leading to alterations in plant diversity, community composition, and ecosystem functioning. For herbaceous understorey communities in temperate forests, responses to global change are postulated to be complex, due to the presence of a tree layer that modulates understorey responses to external pressures such as climate change and changes in atmospheric nitrogen deposition rates. Multiple investigative approaches have been put forward as tools to detect, quantify and predict understorey responses to these global-change drivers, including, among others, distributed resurvey studies and manipulative experiments. These investigative approaches are generally designed and reported upon in isolation, while integration across investigative approaches is rarely considered. In this study, we integrate three investigative approaches (two complementary resurvey approaches and one experimental approach) to investigate how climate warming and changes in nitrogen deposition affect the functional composition of the understorey and how functional responses in the understorey are modulated by canopy disturbance, that is, changes in overstorey canopy openness over time. Our resurvey data reveal that most changes in understorey functional characteristics represent responses to changes in canopy openness with shifts in macroclimate temperature and aerial nitrogen deposition playing secondary roles. Contrary to expectations, we found little evidence that these drivers interact. In addition, experimental findings deviated from the observational findings, suggesting that the forces driving understorey change at the regional scale differ from those driving change at the forest floor (i.e., the experimental treatments). Our study demonstrates that different approaches need to be integrated to acquire a full picture of how understorey communities respond to global change.


Assuntos
Ecossistema , Florestas , Árvores , Plantas , Nitrogênio
3.
Glob Chang Biol ; 30(1): e17104, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38273555

RESUMO

Globally pervasive increases in atmospheric CO2 and nitrogen (N) deposition could have substantial effects on plant communities, either directly or mediated by their interactions with soil nutrient limitation. While the direct consequences of N enrichment on plant communities are well documented, potential interactions with rising CO2 and globally widespread phosphorus (P) limitation remain poorly understood. We investigated the consequences of simultaneous elevated CO2 (eCO2 ) and N and P additions on grassland biodiversity, community and functional composition in P-limited grasslands. We exposed soil-turf monoliths from limestone and acidic grasslands that have received >25 years of N additions (3.5 and 14 g m-2 year-1 ) and 11 (limestone) or 25 (acidic) years of P additions (3.5 g m-2 year-1 ) to eCO2 (600 ppm) for 3 years. Across both grasslands, eCO2 , N and P additions significantly changed community composition. Limestone communities were more responsive to eCO2 and saw significant functional shifts resulting from eCO2 -nutrient interactions. Here, legume cover tripled in response to combined eCO2 and P additions, and combined eCO2 and N treatments shifted functional dominance from grasses to sedges. We suggest that eCO2 may disproportionately benefit P acquisition by sedges by subsidising the carbon cost of locally intense root exudation at the expense of co-occurring grasses. In contrast, the functional composition of the acidic grassland was insensitive to eCO2 and its interactions with nutrient additions. Greater diversity of P-acquisition strategies in the limestone grassland, combined with a more functionally even and diverse community, may contribute to the stronger responses compared to the acidic grassland. Our work suggests we may see large changes in the composition and biodiversity of P-limited grasslands in response to eCO2 and its interactions with nutrient loading, particularly where these contain a high diversity of P-acquisition strategies or developmentally young soils with sufficient bioavailable mineral P.


Assuntos
Dióxido de Carbono , Pradaria , Dióxido de Carbono/análise , Fósforo , Plantas , Poaceae , Nitrogênio , Solo/química , Carbonato de Cálcio
4.
PLoS One ; 18(10): e0290843, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37792796

RESUMO

A common practice used to restore and maintain biodiversity in grasslands is to stop or decrease the use of fertilizers as they are a major cause of biodiversity loss. This practice is problematic for farmers who need fertilizers to increase forage and meet the nutritional needs of livestock. Evidence is needed that helps identify optimal fertilizer regimes that could benefit biodiversity and livestock production simultaneously over the long-term. Here, we evaluated the impact of different fertilizer regimes on indicators related to both biodiversity (plant, pollinator, leaf miners and parasitoid Shannon-Weiner diversity, bumblebee abundance, nectar productivity and forb species richness), and forage production (ash, crude protein, ruminant metabolizable energy and dry matter). To this end, we used data from a grassland restoration experiment managed under four nutrient inputs schemes for 27 years: farmyard manure (FYM; 72 kg N ha-1 yr-1), artificial nitrogen-phosphorus and potassium (NPK; 25 kg N ha-1 yr-1), FYM + NPK (97 kg N ha-1 yr-1) and no-fertilizer. Results showed strong trade-offs between biodiversity and forage production under all treatments even in applications lower than the critical load in the EU. Overall, farmyard manure was the fertilizer that optimized production and biodiversity while 97 kg N ha-1 yr-1 of fertilizer addition (FYM+NPK) had the most negative impact on biodiversity. Finally, forage from places where no fertilizer has been added for 27 years did not meet the nutritional requirements of cattle, but it did for sheep. Rethinking typical approaches of nutrient addition could lead to land management solutions suitable for biological conservation and agriculture.


Assuntos
Pradaria , Esterco , Bovinos , Animais , Ovinos , Fertilizantes , Agricultura/métodos , Biodiversidade , Nitrogênio/metabolismo , Gado/metabolismo , Fertilização , Solo
5.
Sci Total Environ ; 861: 160660, 2023 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-36464051

RESUMO

Extreme weather events are increasing in frequency and magnitude with profound effects on ecosystem functioning. Further, there is now a greater likelihood that multiple extreme events are occurring within a single year. Here we investigated the effect of a single drought, flood or compound (flood + drought) extreme event on temperate grassland ecosystem processes in a field experiment. To assess system resistance and resilience, we studied changes in a wide range of above- and below-ground indicators (plant diversity and productivity, greenhouse gas emissions, soil chemical, physical and biological metrics) during the 8 week stress events and then for 2 years post-stress. We hypothesized that agricultural grasslands would have different degrees of resistance and resilience to flood and drought stress. We also investigated two alternative hypotheses that the combined flood + drought treatment would either, (A) promote ecosystem resilience through more rapid recovery of soil moisture conditions or (B) exacerbate the impact of the single flood or drought event. Our results showed that flooding had a much greater effect than drought on ecosystem processes and that the grassland was more resistant and resilient to drought than to flood. The immediate impact of flooding on all indicators was negative, especially for those related to production, and climate and water regulation. Flooding stress caused pronounced and persistent shifts in soil microbial and plant communities with large implications for nutrient cycling and long-term ecosystem function. The compound flood + drought treatment failed to show a more severe impact than the single extreme events. Rather, there was an indication of quicker recovery of soil and microbial parameters suggesting greater resilience in line with hypothesis (A). This study clearly reveals that contrasting extreme weather events differentially affect grassland ecosystem function but that concurrent events of a contrasting nature may promote ecosystem resilience to future stress.


Assuntos
Ecossistema , Clima Extremo , Pradaria , Plantas , Solo/química , Secas
6.
New Phytol ; 235(5): 2046-2053, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35622460

RESUMO

Mature temperate woodlands are commonly dominated by ectomycorrhizal trees, whereas understory plants predominantly form arbuscular mycorrhizal associations. Due to differences in plant-fungus compatibility between canopy and ground layer vegetation the 'mycorrhizal mediation hypothesis' predicts that herbaceous plant establishment may be limited by a lack of suitable mycorrhizal fungal inoculum. We examined plant species data for 103 woodlands across Great Britain recorded in 1971 and in 2000 to test whether herbaceous plant species richness was related to the proportion of arbuscular mycorrhizal woody plants. We compared the effect of mycorrhizal type with other important drivers of woodland plant species richness. We found a positive effect of the relative abundance of arbuscular mycorrhizal woody plants on herbaceous plant species richness. The size of the observed effect was smaller than that of pH. Moreover, the effect persisted over time, despite many woodlands undergoing marked successional change and increased understorey shading. This work supports the mycorrhizal mediation hypothesis in British woodlands and suggests that increased abundance of arbuscular mycorrhizal woody plants is associated with greater understory plant species richness.


Assuntos
Micorrizas , Florestas , Plantas/microbiologia , Árvores/microbiologia , Madeira
7.
Philos Trans R Soc Lond B Biol Sci ; 377(1853): 20210172, 2022 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-35491602

RESUMO

Research into pollinators in managed landscapes has recently combined approaches of pollination ecology and landscape ecology, because key stressors are likely to interact across wide areas. While laboratory and field experiments are valuable for furthering understanding, studies are required to investigate the interacting drivers of pollinator health and diversity across a broader range of landscapes and a wider array of taxa. Here, we use a network of 96 study landscapes in six topographically diverse regions of Britain, to test the combined importance of honeybee density, insecticide loadings, floral resource availability and habitat diversity to pollinator communities. We also explore the interactions between these drivers and the cover and proximity of semi-natural habitat. We found that among our four drivers, only honeybee density was positively related to wild pollinator abundance and diversity, and the positive association between abundance and floral resources depended on insecticide loadings and habitat diversity. By contrast, our exploratory models including habitat composition metrics revealed a complex suite of interactive effects. These results demonstrate that improving pollinator community composition and health is unlikely to be achieved with general resource enhancements only. Rather, local land-use context should be considered in fine-tuning pollinator management and conservation. This article is part of the theme issue 'Natural processes influencing pollinator health: from chemistry to landscapes'.


Assuntos
Agricultura , Inseticidas , Animais , Abelhas , Ecologia , Ecossistema , Polinização
8.
Nanoscale ; 14(6): 2221-2229, 2022 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-35088796

RESUMO

The practical applications of metal-organic frameworks (MOFs) usually require their assembly into mechanically robust structures, usually achieved via coating onto various types of substrates. This paper describes a simple, scalable, and versatile mechanochemical technique for producing MOF nanocrystal coatings on various non-prefunctionalised substrates, including ZrO2, carbon cloth, porous polymer, nickel foam, titanium foil and fluorine-doped tin oxide glass. We revealed the detailed mechanisms that ensure the coating's stability, and identified the coating can facilitate the interfacial energy transfer, which allowed the electrocatalysis application of the MOF coating on conductive substrates. We further demonstrated that coatings can be directly generated in a one-pot fashion by ball milling MOF precursors with substrates.

9.
Chemosphere ; 288(Pt 3): 132612, 2022 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-34678348

RESUMO

Forward osmosis membrane bioreactors (FOMBRs) are currently gaining attention from the wastewater treatment industry, for their potential to produce high effluent quality and a relatively better flux stability against fouling. However, only using physical cleaning methods is not sufficient to recover the water flux performance satisfactorily under a long-term operation. This study comprehensively investigated the efficiency of a hybrid, environmentally-friendly cleaning strategy involving a combination of physical and free nitrous acid (FNA) cleanings under a long-term FOMBR operation. During 92 days of FOMBR operation, physical cleaning recovered the water flux by 85%, whilst FNA cleaning contributed to an additional 5% of the recovery. In addition, FNA cleaning also offered a retardation of fouling deposition by maintaining the water flux 18-30% more than that obtained by only the physical cleaning. A possible mechanism for FNA's role as the cleaning reagent was proposed for the first time in this study based on the water flux performance and membrane autopsy analysis. The results showed FNA cleaning broke down the residual fouling layer, preferencing protein-based substances. A lower ratio of protein to polysaccharides of the residual fouling layer contributed to a more negatively charged membrane surface (- 42.34 ± 0.30 mV) compared to the virgin one (- 17.54 ± 0.81 mV). This resulted in a stronger electrostatic repulsion between the foulants and the membrane surface, and thus slowed down the biofouling deposition process. This study suggested FNA solution has the great potential not only to recover the membrane performance, also as a strategy to slow down fouling deposition.


Assuntos
Incrustação Biológica , Purificação da Água , Incrustação Biológica/prevenção & controle , Reatores Biológicos , Membranas Artificiais , Osmose , Salinidade , Águas Residuárias
10.
Angew Chem Int Ed Engl ; 61(4): e202112880, 2022 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-34694675

RESUMO

The melting behaviour of metal-organic frameworks (MOFs) has aroused significant research interest in the areas of materials science, condensed matter physics and chemical engineering. This work first introduces a novel method to fabricate a bimetallic MOF glass, through melt-quenching of the cobalt-based zeolitic imidazolate framework (ZIF) [ZIF-62(Co)] with an adsorbed ferric coordination complex. The high-temperature chemically reactive ZIF-62(Co) liquid facilitates the formation of coordinative bonds between Fe and imidazolate ligands, incorporating Fe nodes into the framework after quenching. The resultant Co-Fe bimetallic MOF glass therefore shows a significantly enhanced oxygen evolution reaction performance. The novel bimetallic MOF glass, when combined with the facile and scalable mechanochemical synthesis technique for both discrete powders and surface coatings on flexible substrates, enables significant opportunities for catalytic device assembly.

11.
Membranes (Basel) ; 11(5)2021 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-33946958

RESUMO

Nanodiamonds (ND) have recently emerged as excellent candidates for various applications including membrane technology due to their nanoscale size, non-toxic nature, excellent mechanical and thermal properties, high surface areas and tuneable surface structures with functional groups. However, their non-porous structure and strong tendency to aggregate are hindering their potential in gas separation membrane applications. To overcome those issues, this study proposes an efficient approach by decorating the ND surface with polyethyleneimine (PEI) before embedding it into the polymer matrix to fabricate MMMs for CO2/N2 separation. Acting as both interfacial binder and gas carrier agent, the PEI layer enhances the polymer/filler interfacial interaction, minimising the agglomeration of ND in the polymer matrix, which is evidenced by the focus ion beam scanning electron microscopy (FIB-SEM). The incorporation of PEI into the membrane matrix effectively improves the CO2/N2 selectivity compared to the pristine polymer membranes. The improvement in CO2/N2 selectivity is also modelled by calculating the interfacial permeabilities with the Felske model using the gas permeabilities in the MMM. This study proposes a simple and effective modification method to address both the interface and gas selectivity in the application of nanoscale and non-porous fillers in gas separation membranes.

12.
R Soc Open Sci ; 8(2): 201150, 2021 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-33972848

RESUMO

This research involved carrying out a unique micro-mesoporous carbon particle incorporation into P84 co-polyimide membrane for improved gas separation performance. The carbon filler was prepared using a hard template method from zeolite and known as zeolite-templated carbon (ZTC). This research aims to study the loading amount of ZTC into P84 co-polyimide toward the gas separation performance. The ZTC was prepared using simple impregnation method of sucrose into hard template of zeolite Y. The SEM result showing a dispersed ZTC particle on the membrane surface and cross-section. The pore size distribution (PSD) of ZTC revealed that the particle consists of two characteristics of micro and mesoporous region. It was noted that with only 0.5 wt% of ZTC addition, the permeability was boosted up from 4.68 to 7.06 and from 8.95 to 13.15 barrer, for CO2 and H2 respectively when compared with the neat membrane. On the other hand, the optimum loading was at 1 wt%, where the membrane received thermal stability boost of 10% along with the 62.4 and 35% of selectivity boost of CO2/CH4 and H2/CH4, respectively. It was noted that the position of the filler on the membrane surface was significantly affecting the gas transport mechanism of the membrane. Overall, the results demonstrated that the addition of ZTC with proper filler position is a potential candidate to be applicable in the gas separation involving CO2 and H2.

13.
Environ Pollut ; 281: 117017, 2021 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-33813199

RESUMO

The effects of atmospheric pollution on plant species richness (nsp) are of widespread concern. We carried out a modelling exercise to estimate how nsp in British semi-natural ecosystems responded to atmospheric deposition of nitrogen (Ndep) and sulphur (Sdep) between 1800 and 2010. We derived a simple four-parameter equation relating nsp to measured soil pH, and to net primary productivity (NPP), calculated with the N14CP ecosystem model. Parameters were estimated from a large data set (n = 1156) of species richness in four vegetation classes, unimproved grassland, dwarf shrub heath, peatland, and broadleaved woodland, obtained in 2007. The equation performed reasonably well in comparisons with independent observations of nsp. We used the equation, in combination with modelled estimates of NPP (from N14CP) and soil pH (from the CHUM-AM hydrochemical model), to calculate changes in average nsp over time at seven sites across Britain, assuming that variations in nsp were due only to variations in atmospheric deposition. At two of the sites, two vegetation classes were present, making a total of nine site/vegetation combinations. In four cases, nsp was affected about equally by pH and NPP, while in another four the effect of pH was dominant. The ninth site, a chalk grassland, was affected only by NPP, since soil pH was assumed constant. Our analysis suggests that the combination of increased NPP, due to fertilization by Ndep, and decreased soil pH, primarily due to Sdep, caused an average species loss of 39% (range 23-100%) between 1800 and the late 20th Century. The modelling suggests that in recent years nsp has begun to increase, almost entirely due to reductions in Sdep and consequent increases in soil pH, but there are also indications of recent slight recovery from the eutrophying effects of Ndep.


Assuntos
Ecossistema , Plantas , Florestas , Nitrogênio/análise , Solo
14.
PeerJ ; 9: e10632, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33520449

RESUMO

Estimation of the impacts of atmospheric nitrogen (N) deposition on ecosystems and biodiversity is a research imperative. Analyses of large-scale spatial gradients, where an observed response is correlated with measured or modelled deposition, have been an important source of evidence. A number of problems beset this approach. For example, if responses are spatially aggregated then treating each location as statistically independent can lead to biased confidence intervals and a greater probably of false positive results. Using methods that account for residual spatial autocorrelation, Pescott & Jitlal (2020) re-analysed two large-scale spatial gradient datasets from Britain where modelled N deposition at 5 × 5 km resolution had been previously correlated with species richness in small quadrats. They found that N deposition effects were weaker than previously demonstrated leading them to conclude that "previous estimates of Ndep impacts on richness from space-for-time substitution studies are likely to have been over-estimated". We use a simulation study to show that their conclusion is unreliable despite them recognising that an influential fraction of the residual spatially structured variation could itself be attributable to N deposition. This arises because the covariate used was modelled N deposition at 5 × 5 km resolution leaving open the possibility that measured or modelled N deposition at finer resolutions could explain more variance in the response. Explicitly treating this as spatially auto-correlated error ignores this possibility and leads directly to their unreliable conclusion. We further demonstrate the plausibility of this scenario by showing that significant variation in N deposition at the 1 km square resolution is indeed averaged at 5 × 5 km resolution. Further analyses are required to explore whether estimation of the size of the N deposition effect on plant species richness and other measures of biodiversity is indeed dependent on the accuracy and hence measurement error of the N deposition covariate. Until then the conclusions of Pescott & Jitlal (2020) should be considered premature.

15.
J Anim Ecol ; 90(2): 404-414, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-33067860

RESUMO

Grassland fertilisation drives non-random plant loss resulting in areas dominated by perennial grass species. How these changes cascade through linked trophic levels, however, is not well understood. We studied how grassland fertilisation propagates change through the plant assemblage into the plant-flower-visitor, plant-leaf miner and leaf miner-parasitoid networks using a year's data collection from a long-term grassland fertiliser application experiment. Our experiment had three fertiliser treatments each applied to replicate plots 15 m2 in size: mineral fertiliser, farmyard manure, and mineral fertiliser and farmyard manure combined, along with a control of no fertiliser. The combined treatment had the most significant impact, and both plant species richness and floral abundance decreased with the addition of fertiliser. While insect species richness was unaffected by fertiliser treatment, fertilised plots had a significantly higher abundance of leaf miners and parasitoids and a significantly lower abundance of bumblebees. The plant-flower-visitor and plant-herbivore networks showed higher values of vulnerability and lower modularity with fertiliser addition, while leaf miner-parasitoid networks showed a rise in generality. The different groups of insects were impacted by fertilisers to varying degrees: while the effect on abundance was the highest for leaf miners, the vulnerability and modularity of flower-visitor networks was the most affected. The impact on the abundance of leaf miners was positive and three times higher than the impact on parasitoids, and the impact on bumblebee abundance was negative and double the magnitude of impact on flower abundance. Overall, our results show that while insect species richness was unaffected by fertilisers, network structure changed significantly as the replacement of forbs by grasses resulted in changes in relative abundance across trophic levels, with the direction of change depending on the type of network. Synthesis. By studying multiple networks simultaneously, we were able to rank the relative impact of habitat change on the different groups of species within the community. This provided a more holistic picture of the impact of agricultural intensification and provides useful information when deciding on priorities for mitigation.


Assuntos
Fertilizantes , Polinização , Animais , Abelhas , Ecossistema , Insetos , Plantas
16.
Chemosphere ; 260: 127581, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32758787

RESUMO

Forward osmosis membrane bioreactor (FOMBR) is an integrated physical-biological treatment process that has received increased awareness in treating municipal wastewater for its potential to produce high effluent quality coupled with its low propensity for fouling formation. However, reverse salt diffusion (RSD) is a major issue and so far limited studies have reported long-term FOMBR operation under the elevated salinity conditions induced by RSD. This study investigated the performance of a FOMBR in treating municipal wastewater under a controlled saline environment (6-8 g L-1 NaCl) using two separate sodium chloride draw solution (NaCl DS) concentrations (35 and 70 g L-1) over 243 days. At 35 g L-1 NaCl DS, the water flux performance dropped from 6.75 L m-2 h-1 (LMH) to 2.07 LMH after 72 days of operation in the first experimental stage, when no cleaning procedure was implemented. In the subsequent stage, the DS concentration was increased to 70 g L-1 and a weekly physical cleaning regime introduced. Under stable operation, the water flux performance recovery was 67% after 21 cycles of physical cleaning. For the first time in FOMBR studies, a shortcut nitrogen removal via the nitrite pathway was also achieved under the elevated salinity conditions. At the end of operation (day 243), the ammonia-oxidising bacteria (Nitrosomonas sp.) was the only nitrifier species in the system and no nitrite oxidising bacteria was detected. The above study proves that a FOMBR system is a feasible process for treating municipal wastewater.


Assuntos
Membranas Artificiais , Nitrogênio/metabolismo , Eliminação de Resíduos Líquidos/instrumentação , Eliminação de Resíduos Líquidos/métodos , Aerobiose , Reatores Biológicos/microbiologia , Desnitrificação , Desenho de Equipamento , Nitrificação , Nitritos/metabolismo , Nitrosomonas/metabolismo , Osmose , Salinidade , Águas Residuárias/química
17.
J Chem Phys ; 153(3): 034107, 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32716189

RESUMO

We present NECI, a state-of-the-art implementation of the Full Configuration Interaction Quantum Monte Carlo (FCIQMC) algorithm, a method based on a stochastic application of the Hamiltonian matrix on a sparse sampling of the wave function. The program utilizes a very powerful parallelization and scales efficiently to more than 24 000 central processing unit cores. In this paper, we describe the core functionalities of NECI and its recent developments. This includes the capabilities to calculate ground and excited state energies, properties via the one- and two-body reduced density matrices, as well as spectral and Green's functions for ab initio and model systems. A number of enhancements of the bare FCIQMC algorithm are available within NECI, allowing us to use a partially deterministic formulation of the algorithm, working in a spin-adapted basis or supporting transcorrelated Hamiltonians. NECI supports the FCIDUMP file format for integrals, supplying a convenient interface to numerous quantum chemistry programs, and it is licensed under GPL-3.0.

18.
ACS Appl Mater Interfaces ; 12(19): 21670-21681, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-32309923

RESUMO

The efficient CO2 electrochemical reduction reaction (CO2RR) relies not only on the development of selective/active catalysts but also on the advanced electrode configuration to solve the critical issue of poor CO2 mass transport and derived sluggish cathodic reaction kinetics. In this work, to achieve a favorable reaction rate and product selectivity, we designed and synthesized an asymmetric porous Cu hollow fiber gas diffusion electrode (HFGDE) with controlled Sn surface electrodeposition. The HFGDE derived from the optimal Sn electrodeposition condition exhibited a formate Faradaic efficiency (FE) of 78% and a current density of 88 mA cm-2 at -1.2 V versus reversible hydrogen electrode, which are more than 2 times higher than those from the pristine Cu HFGDE. The achieved performance outperformed most of the other Sn-based GDEs, indicating the creation of sufficient contact among CO2, electrolyte, and electrode catalyst through the design of the hollow fiber pore structure and catalytic active sites. The enhancement of formate production selectivity and the suppression of the hydrogen by-product were attributed to the optimized ratio of SnOx species on the electrode surface. The best performance was seen in the HFGDE with the highest Sn2+/Sn4+ (120 s deposition), likely due to the modulating effect of the Cu substrate via electron donation with Sn species. The selectivity control strategy developed in the asymmetric HFGDE provides an efficient and facile method to stimulate selective electrochemical reactions in which the gas-phase reactant with low solubility is involved.

19.
Chem Commun (Camb) ; 56(25): 3609-3612, 2020 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-32167111

RESUMO

Non-stoichoimetric crystalline ZIF-62 was used as the filler for a 6FDA-DAM polyimide-based composite membrane. In situ melting and vitrification of ZIF-62 was then performed, to yield the ZIF-62 glass phase (agZIF-62), within the polymer matrix. Focus ion beam scanning electron microscopy (FIB-SEM), thermal characterisation and membrane separation tests demonstrate the filling of voids at the MOF/polymer interface from the liquid phase of ZIF-62.

20.
Ecol Evol ; 9(22): 12858-12868, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31788220

RESUMO

Quantitative models play an increasing role in exploring the impact of global change on biodiversity. To win credibility and trust, they need validating. We show how expert knowledge can be used to assess a large number of empirical species niche models constructed for the British vascular plant and bryophyte flora. Key outcomes were (a) scored assessments of each modeled species and niche axis combination, (b) guidance on models needing further development, (c) exploration of the trade-off between presenting more complex model summaries, which could lead to more thorough validation, versus the longer time these take to evaluate, (d) quantification of the internal consistency of expert opinion based on comparison of assessment scores made on a random subset of models evaluated by both experts. Overall, the experts assessed 39% of species and niche axis combinations to be "poor" and 61% to show a degree of reliability split between "moderate" (30%), "good" (25%), and "excellent" (6%). The two experts agreed in only 43% of cases, reaching greater consensus about poorer models and disagreeing most about models rated as better by either expert. This low agreement rate suggests that a greater number of experts is required to produce reliable assessments and to more fully understand the reasons underlying lack of consensus. While area under curve (AUC) statistics showed generally very good ability of the models to predict random hold-out samples of the data, there was no correspondence between these and the scores given by the experts and no apparent correlation between AUC and species prevalence. Crowd-sourcing further assessments by allowing web-based access to model fits is an obvious next step. To this end, we developed an online application for inspecting and evaluating the fit of each niche surface to its training data.

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