Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C2xB1−xN1−x alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C (x < 0.25); and (b) the electronic structure of C2xB1−xN1−x can be further tuned not only with composition x, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C2xB1−xN1−x alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

Climate justice in a carbon budget

The fact of a carbon budget given commitment to limiting global-mean temperature increase to below 2°C warming relative to pre-industrial levels makes CO2 emissions a scarce resource. This fact has significant consequences for the ethics of climate change. The paper highlights some of these consequences with respect to (a) applying principles of distributive justice to the allocation of rights to emissions and the costs of mitigation and adaptation, (b) compensation for the harms and risks of climate change, (c) radical new ideas about a place for criminal justice in tackling climate change, and (d) catastrophe ethics.

Joint data assimilation of satellite reflectance and net ecosystem exchange data constrains ecosystem carbon fluxes at a high-elevation subalpine forest

We utilized an ecosystem process model (SIPNET, simplified photosynthesis and evapotranspiration model) to estimate carbon fluxes of gross primary productivity and total ecosystem respiration of a high-elevation coniferous forest. The data assimilation routine incorporated aggregated twice-daily measurements of the net ecosystem exchange of CO2 (NEE) and satellite-based reflectance measurements of the fraction of absorbed photosynthetically active radiation (fAPAR) on an eight-day timescale. From these data we conducted a data assimilation experiment with fifteen different combinations of available data using twice-daily NEE, aggregated annual NEE, eight-day f AP AR, and average annual fAPAR. Model parameters were conditioned on three years of NEE and fAPAR data and results were evaluated to determine the information content from the different combinations of data streams. Across the data assimilation experiments conducted, model selection metrics such as the Bayesian Information Criterion and Deviance Information Criterion obtained minimum values when assimilating average annual fAPAR and twice-daily NEE data. Application of wavelet coherence analyses showed higher correlations between measured and modeled fAPAR on longer timescales ranging from 9 to 12 months. There were strong correlations between measured and modeled NEE (R2, coefficient of determination, 0.86), but correlations between measured and modeled eight-day fAPAR were quite poor (R2 = −0.94). We conclude that this inability to determine fAPAR on eight-day timescale would improve with the considerations of the radiative transfer through the plant canopy. Modeled fluxes when assimilating average annual fAPAR and annual NEE were comparable to corresponding results when assimilating twice-daily NEE, albeit at a greater uncertainty. Our results support the conclusion that for this coniferous forest twice-daily NEE data are a critical measurement stream for the data assimilation. The results from this modeling exercise indicate that for this coniferous forest, average annuals for satellite-based fAPAR measurements paired with annual NEE estimates may provide spatial detail to components of ecosystem carbon fluxes in proximity of eddy covariance towers. Inclusion of other independent data streams in the assimilation will also reduce uncertainty on modeled values.

Simple measures of climate, soil properties and plant traits predict national scale grassland soil carbon stocks

1. Soil carbon (C) storage is a key ecosystem service. Soil C stocks play a vital role in soil fertility and climate regulation, but the factors that control these stocks at regional and national scales are unknown, particularly when their composition and stability are considered. As a result, their mapping relies on either unreliable proxy measures or laborious direct measurements. 2. Using data from an extensive national survey of English grasslands we show that surface soil (0-7cm) C stocks in size fractions of varying stability can be predicted at both regional and national scales from plant traits and simple measures of soil and climatic conditions. 3. Soil C stocks in the largest pool, of intermediate particle size (50-250 µm), were best explained by mean annual temperature (MAT), soil pH and soil moisture content. The second largest C pool, highly stable physically and biochemically protected particles (0.45-50 µm), was explained by soil pH and the community abundance weighted mean (CWM) leaf nitrogen (N) content, with the highest soil C stocks under N rich vegetation. The C stock in the small active fraction (250-4000 µm) was explained by a wide range of variables: MAT, mean annual precipitation, mean growing season length, soil pH and CWM specific leaf area; stocks were higher under vegetation with thick and/or dense leaves. 4. Testing the models describing these fractions against data from an independent English region indicated moderately strong correlation between predicted and actual values and no systematic bias, with the exception of the active fraction, for which predictions were inaccurate. 5. Synthesis and Applications: Validation indicates that readily available climate, soils and plant survey data can be effective in making local- to landscape-scale (1-100,000 km2) soil C stock predictions. Such predictions are a crucial component of effective management strategies to protect C stocks and enhance soil C sequestration.

What is Carbon? Conceptualising carbon and capabilities in the context of community sequestration projects in the global South

Carbon has been described as a ‘surreal commodity’. Whilst carbon trading, storage, sequestration and emissions have become a part of the contemporary climate lexicon, how carbon is understood, valued and interpreted by actors responsible for implementing carbon sequestration projects is still unclear. In this review paper, we are concerned with how carbon has come to take on a range of meanings, and in particular, we appraise what is known about the situated meanings that people involved in delivering, and participating in, carbon sequestration projects in the global South assign to this complex element. Whilst there has been some reflection on the new meanings conferred on carbon via the neoliberal processes of marketisation, and how these processes interact with historical and contemporary narratives of environmental change, less is known about how these meanings are (re)produced and (re)interpreted locally. We review how carbon has been defined both as a chemical element and as a tradable, marketable commodity, and discuss the implications these global meanings might have for situated understandings, particularly linked to climate change narratives, amongst communities in the global South. We consider how the concept of carbon capabilities, alongside theoretical notions of networks, assemblages and local knowledges of the environment and nature, might be useful in beginning to understand how communities engage with abstract notions of carbon. We discuss the implications of specific values attributed to carbon, and therefore to different ecologies, for wider conceptualisations of how nature is valued, and climate is understood, and particularly how this may impact on community interactions with carbon sequestration projects. Knowing more about how people understand, value and know carbon allows policies to be better informed and practices more effectively targeted at engaging local populations meaningfully in carbon-related projects.

An investigation of the required skills for the delivery of low and zero carbon buildings within a region

The United Kingdom is committed to a raft of requirements to create a low-carbon economy. Buildings consume approximately 40% of UK energy demand. Any improvement on the energy performance of buildings therefore can significantly contribute to the delivery of a low-carbon economy. The challenge for the construction sector and its clients is how to meet the policy requirements to deliver low and zero carbon (LZC) buildings, which spans broader than the individual building level, to requirements at the local and regional levels, and wider sustainability pressures. Further, the construction sector is reporting skills shortages coupled with the need for ‘new skills’ for the delivery of LZC buildings. The aim of this paper is to identify, and better understand, the skills required by the construction sector and its clients for the delivery of LZC buildings within a region. The theoretical framing for this research is regional innovation system (RIS) using a socio-technical network analysis (STNA) methodology. A case study of a local authority region is presented. Data is drawn from a review of relevant local authority documentation, observations and semi-structured interviews from one (project 1) of five school retrofit projects within the region. The initial findings highlight the complexity surrounding the form and operation of the LZC network for project 1. The skills required by the construction sector and its clients are connected to different actor roles surrounding the delivery of the project. The key actors involved and their required skills are: project management and energy management skills required by local authority; project management skills (in particular project planning), communication and research skills required by school end-users; and a ‘technical skill’ relating to knowledge of a particular energy efficient measure (EEM) and use of equipment to implement the EEM is required by the EEM contractors.

Including an ocean carbon cycle model into iLOVECLIM (v1.0)

The atmospheric carbon dioxide concentration plays a crucial role in the radiative balance and as such has a strong influence on the evolution of climate. Because of the numerous interactions between climate and the carbon cycle, it is necessary to include a model of the carbon cycle within a climate model to understand and simulate past and future changes of the carbon cycle. In particular, natural variations of atmospheric CO2 have happened in the past, while anthropogenic carbon emissions are likely to continue in the future. To study changes of the carbon cycle and climate on timescales of a few hundred to a few thousand years, we have included a simple carbon cycle model into the iLOVECLIM Earth System Model. In this study, we describe the ocean and terrestrial biosphere carbon cycle models and their performance relative to observational data. We focus on the main carbon cycle variables including the carbon isotope ratios δ13C and the Δ14C. We show that the model results are in good agreement with modern observations both at the surface and in the deep ocean for the main variables, in particular phosphates, dissolved inorganic carbon and the carbon isotopes.

The hidden organic carbon in deep mineral soils

Aims Current estimates of soil organic carbon (SOC) are based largely on surficial measurements to depths of 0.3 to 1 m. Many of the world’s soils greatly exceed 1 m depth and there are numerous reports of biological activity to depths of many metres. Although SOC storage to depths of up to 8 m has been previously reported, the extent to which SOC is stored at deeper depths in soil profiles is currently unknown. This paper aims to provide the first detailed analysis of these previously unreported stores of SOC. Methods Soils from five sites in the deeply weathered regolith in the Yilgarn Craton of south-western Australia were sampled and analysed for total organic carbon by combustion chromatography. These soils ranged between 5 and 38 m (mean 21 m) depth to bedrock and had been either recently reforested with Pinus pinaster or were under agriculture. Sites had a mean annual rainfall of between 399 and 583 mm yr−1. Results The mean SOC concentration across all sites was 2.30 ± 0.26 % (s.e.), 0.41 ± 0.05 % and 0.23 ± 0.04 % in the surface 0.1, 0.1–0.5 and 0.5 to 1.0 m increments, respectively. The mean value between 1 and 5 m was 0.12 ± 0.01 %, whereas between 5 and 35 m the values decreased from 0.04 ± 0.002 % to 0.03 ± 0.003 %. Mean SOC mass densities for each of the five locations varied from 21.8–37.5 kg C m−2, and were in toto two to five times greater than would be reported with sampling to a depth of 0.5 m. Conclusions This finding may have major implications for estimates of global carbon storage and modelling of the potential global impacts of climate change and land-use change on carbon cycles. The paper demonstrates the need for a reassessment of the current arbitrary shallow soil sampling depths for assessing carbon stocks, a revision of global SOC estimates and elucidation of the composition and fate of deep carbon in response to land use and climate change

Reforesting degraded agricultural landscapes with Eucalypts: effects on carbon storage and soil fertility after 26years

In the Western Australian wheatbelt, the restoration of native eucalypt forests for managing degraded agricultural landscapes is a critical part of managing dryland salinity and rebuilding biodiversity. Such reforestation will also sequester carbon. Whereas most investigative emphasis has been on carbon stored in biomass, the effects of reforestation on soil organic carbon (SOC) stores and fertility are not known. Two 26 year old reforestation experiments with four Eucalyptus species (E. cladocalyx var nana, E. occidentalis, E. sargentii and E. wandoo) were compared with agricultural sites (Field). SOC stores (to 0.3 m depth) ranged between 33 and 55 Mg ha−1, with no statistically significant differences between tree species and adjacent farmland. Farming comprised crop and pasture rotations. In contrast, the reforested plots contained additional carbon in the tree biomass (23–60 Mg ha−1) and litter (19–34 Mg ha−1), with the greatest litter accumulation associated with E. sargentii. Litter represented between 29 and 56% of the biomass carbon and the protection or utilization of this litter in fire-prone, semi-arid farmland will be an important component of carbon management. Exch-Na and Exch-Mg accumulated under E. sargentii and E. occidentalis at one site. The results raise questions about the conclusions of SOC sequestration studies following reforestation based on limited sampling and reiterate the importance of considering litter in reforestation carbon accounts.

A sustainable agricultural landscape for Australia: A review of interlacing carbon sequestration, biodiversity and salinity management in agroforestry systems

Transformation of the south-western Australian landscape from deep-rooted woody vegetation systems to shallow-rooted annual cropping systems has resulted in the severe loss of biodiversity and this loss has been exacerbated by rising ground waters that have mobilised stored salts causing extensive dry land salinity. Since the original plant communities were mostly perennial and deep rooted, the model for sustainable agriculture and landscape water management invariably includes deep rooted trees. Commercial forestry is however only economical in higher rainfall (>700 mm yr−1) areas whereas much of the area where biodiversity is threatened has lower rainfall (300–700 mm yr−1). Agroforestry may provide the opportunity to develop new agricultural landscapes that interlace ecosystem services such as carbon mitigation via carbon sequestration and biofuels, biodiversity restoration, watershed management while maintaining food production. Active markets are developing for some of these ecosystem services, however a lack of predictive metrics and the regulatory environment are impeding the adoption of several ecosystem services. Nonetheless, a clear opportunity exists for four major issues – the maintenance of food and fibre production, salinisation, biodiversity decline and climate change mitigation – to be managed at a meaningful scale and a new, sustainable agricultural landscape to be developed.

Soil carbon and litter development along a reconstructed biodiverse forest chronosequence of South-Western Australia

Soil organic matter (SOM) increases with time as landscape is restored. Studying SOM development along restored forest chronosequences would be useful in clarifying some of the uncertainties in quantifying C turnover rates with respect to forest clearance and ensuing restoration. The development of soil organic matter in the mineral soils was studied at four depths in a 16-year-old restored jarrah forest chronosequence. The size-separated SOM fractionation along with δ13C isotopic shift was utilised to resolve the soil C temporal and spatial changes with developing vegetation. The restored forest chronosequence revealed several important insights into how soil C is developing with age. Litter accumulation outpaced the native forest levels in 12 years after restoration. The surface soils, in general, showed increase in total C with age, but this trend was not clearly observed at lower depths. C accumulation was observed with increasing restoration age in all three SOM size-fractions in the surface 0–2 cm depth. These biodiverse forests show a trend towards accumulating C in recalcitrant stable forms, but only in the surface 0–2 cm mineral soil. A significant reverse trend was observed for the moderately labile SOM fraction for lower depths with increasing restoration age. Correlating the soil δ13C with total C concentration revealed the re-establishment of the isotopically depleted labile to enriched refractory C continuum with soil depth for the older restored sites. This implied that from a pedogenic perspective, the restored soils are developing towards the original native soil carbon profile.

Carbon trading for phosphorus gain: the balance between rhizosphere carboxylates and arbuscular mycorrhizal symbiosis in plant phosphorus acquisition

Two key plant adaptations for phosphorus (P) acquisition are carboxylate exudation into the rhizosphere and mycorrhizal symbioses. These target different soil P resources, presumably with different plant carbon costs. We examined the effect of inoculation with arbuscular mycorrhizal fungi (AMF) on amount of rhizosphere carboxylates and plant P uptake for 10 species of low-P adapted Kennedia grown for 23 weeks in low-P sand. Inoculation decreased carboxylates in some species (up to 50%), decreased plant dry weight (21%) and increased plant P content (23%). There was a positive logarithmic relationship between plant P content and the amount of rhizosphere citric acid for inoculated and uninoculated plants. Causality was indicated by experiments using sand where little citric acid was lost from the soil solution over 2 h and citric acid at low concentrations desorbed P into the soil solution. Senesced leaf P concentration was often low and P-resorption efficiencies reached >90%. In conclusion, we propose that mycorrhizally mediated resource partitioning occurred because inoculation reduced rhizosphere carboxylates, but increased plant P uptake. Hence, presumably, the proportion of plant P acquired from strongly sorbed sources decreased with inoculation, while the proportion from labile inorganic P increased. Implications for plant fitness under field conditions now require investigation.

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, 13C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.