Modelling Nitrous Oxide Emissions from Grazed Grasslands in New Zealand

Spatial and temporal variability are major difficulties when quantifying annual N2O fluxes at the field scale. New Zealand currently relies on the IPCC default methodology (National Inventory Report, 2004). This methodology is too simplistic and generalised as it ignores all site-specific controls, but is also not sufficiently flexible to allow mitigation options to be assessed. Therefore, a more robust, process-based approach is required to quantify N2O emissions more accurately at the field level. Denitrification-decomposition (DNDC) is a process-based model originally developed (Li et al., 1992) to quantify agricultural nitrous oxide (N2O) emissions across climatic zones, soil types, and management regimes. This has been modified to represent New Zealand grazed grassland systems (Saggar et al., 2004). More recent modifications include measured biomass C and N parameters in perennial pasture and compaction impacts on the soil water dynamics. Further validation tests have been conducted against observed soil moisture and gas fluxes. Here we i) assess the ability of a modified DNDC model NZ-DNDC to simulate N2O emissions; ii) compare the measured, modelled and IPCCestimated N2O emissions from dairy- and sheep-grazed pastures; and iii) give preliminary results for upscaling the model to provide preliminary regional emissions estimates

Mapping hole mobility in PTB7 films at nanoscale

Funding: Federal Target Program of MES of Russian Federation, contract 14.575.21.0149 (RFMEFI57517X0149).The nanoscale hole mobility in organic semiconducting polymer PTB7 is quantified by using conductive-AFM (C-AFM) measurements in space charge limited (SCLC) regime. The obtained current map of the neat PTB7 film is explained in terms of non-uniform built-in voltage and variations of hole mobility. For mobility estimation, the semi-empirical model of SCLC, known from previous works, was modified and applied. It is found that the values of built-in voltage in C-AFM measurements are usually several times larger than ones derived from macroscopic measurements. It is also shown that value of hole mobility in PTB7 film depends on location and varies in more than two times. These mobility variations are connected with nanoscale film structure revealed by other methods.Publisher PD

Fermi Surface as the Driving Mechanism for Helical Antiferromagnetic Ordering in Gd-Y Alloys

The first direct experimental evidence for the Fermi surface (FS) driving the helical antiferromagnetic ordering in a gadolinium-yttrium alloy is reported. The presence of a FS sheet capable of nesting is revealed, and the nesting vector associated with the sheet is found to be in excellent agreement with the periodicity of the helical ordering.Comment: 4 pages, 4 figure

Barrierless slow dissociation of photogenerated charge pairs in high-performance polymer-fullerene solar cells

The work in St Andrews was supported by the Engineering and Physical Sciences Research Council (grants EP/L017008/1, EP/J009016/1 and EP/G03673X/1) and the European Research Council (grant 321305). The work in Vilnius was supported by the Research Council of Lithuania (project MIP-85/2015). I.D.W.S. acknowledges support from a Royal Society Wolfson Research Merit Award. D.A.V. is grateful to Supergen SuperSolar Hub for the travel grant. The research data supporting this publication can be accessed at http://dx.doi.org/10.17630/7ec84b4b-d2ab-493c-aaf6-5503a44c0eb5Broadband transient absorption spectroscopy is combined with ultrafast carrier drift measurements to study dissociation of photogenerated charge pairs in efficient photovoltaic blends of the electron donating polymer PTB7 with the acceptor PC71BM. A high ensemble-average mobility sum of electrons and holes is observed which is independent of applied electric field above 12 V/μm and indicates nearly barrier-less pair dissociation at room temperature on a picosecond time scale. High efficiency of pair dissociation in this material is achieved by a combination of high electron mobility in fullerene clusters and hole delocalization along the polymer chain which increases by 30% during dissociation. Our results suggest a predominantly diffusive charge pair dissociation mechanism which requires persistent mobility of both carriers and preferably some delocalization of at least one of them.PostprintPostprintPeer reviewe

Self-trapping and excited state absorption in fluorene homo-polymer and copolymers with benzothiadiazole and tri-phenylamine

We thank the EPSRC [EP/J009318/1 and EP/J009016/1] for funding. MJP thanks the European Research Council (ERC) for funding under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC Grant No. 258990.Excited state absorption (ESA) is studied using time-dependent density functional theory and compared with experiments performed in dilute solutions. The molecules investigated are a fluorene pentamer, polyfluorene F8, the alternating F8 copolymer with benzothiadiazole F8BT, and two blue-emitting random copolymers F8PFB and F8TFB. Calculated and measured spectra show qualitatively comparable results. The ESA cross-section of co-polymers at its maximum is about three times lower than that of F8. The ESA spectra are found to change little upon structural relaxation of the excited state, or change in the order of sub-units in a co-polymer, for all studied molecules. In all these molecules, the strongest ESA transition is found to arise from the same electronic process, exhibiting a reversal of the charge parity. In addition, F8PFB and F8TFB are found to possess almost identical electronic behaviour.Publisher PDFPeer reviewe

Seagrass Canopy Photosynthetic Response Is a Function of Canopy Density and Light Environment: A Model for Amphibolis griffithii

A three-dimensional computer model of canopies of the seagrass Amphibolis griffithii was used to investigate the consequences of variations in canopy structure and benthic light environment on leaf-level photosynthetic saturation state. The model was constructed using empirical data of plant morphometrics from a previously conducted shading experiment and validated well to in-situ data on light attenuation in canopies of different densities. Using published values of the leaf-level saturating irradiance for photosynthesis, results show that the interaction of canopy density and canopy-scale photosynthetic response is complex and non-linear, due to the combination of self-shading and the non-linearity of photosynthesis versus irradiance (P-I) curves near saturating irradiance. Therefore studies of light limitation in seagrasses should consider variation in canopy structure and density. Based on empirical work, we propose a number of possible measures for canopy scale photosynthetic response that can be plotted to yield isoclines in the space of canopy density and light environment. These plots can be used to interpret the significance of canopy changes induced as a response to decreases in the benthic light environment: in some cases canopy thinning can lead to an equivalent leaf level light environment, in others physiological changes may also be required but these alone may be inadequate for canopy survival. By providing insight to these processes the methods developed here could be a valuable management tool for seagrass conservation during dredging or other coastal developments

Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems

EZ-C acknowledges the University of St Andrews for financial support. IDWS acknowledges support from EPSRC (EP/J009016) and the European Research Council (grant 321305). IDWS also acknowledges support from a Royal Society Wolfson research merit award. DJ acknowledges the European Research Council (grant: 278845) and the RFI Lumomat for financial support.We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(III) complexes of the form of [Ir(C^N)2(N^N)]PF6 (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (1H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature 1H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations.PostprintPeer reviewe

Redox control of aphid resistance through altered cell wall composition and nutritional quality.

The mechanisms underpinning plant perception of phloem-feeding insects, particularly aphids, remain poorly characterized. Therefore, the role of apoplastic redox state in controlling aphid infestation was explored using transgenic tobacco (Nicotiana tabacum) plants that have either high (PAO) or low (TAO) ascorbate oxidase (AO) activities relative to the wild type. Only a small number of leaf transcripts and metabolites were changed in response to genotype, and cell wall composition was largely unaffected. Aphid fecundity was decreased significantly in TAO plants compared with other lines. Leaf sugar levels were increased and maximum extractable AO activities were decreased in response to aphids in all genotypes. Transcripts encoding the Respiratory Burst Oxidase Homolog F, signaling components involved in ethylene and other hormonemediated pathways, photosynthetic electron transport components, sugar, amino acid, and cell wall metabolism, were increased significantly in the TAO plants in response to aphid perception relative to other lines. The levels of galactosylated xyloglucan were decreased significantly in response to aphid feeding in all the lines, the effect being the least in the TAO plants. Similarly, all lines exhibited increases in tightly bound (1→4)-b-galactan. Taken together, these findings identify AO-dependent mechanisms that limit aphid infestation

‘Preparing Ourselves to Become an International Organization’: Thailand Tobacco Monopoly’s Regional and Global Strategies

The Thailand Tobacco Monopoly (TTM) controlled the country\u27s tobacco industry from its formation in the 1940s, until the government dropped restrictions on imported cigarettes in the late 1980s in response to pressure from the United States. The TTM has since competed with transnational tobacco companies (TTCs) in a semi-monopoly market in which TTCs have steadily increased their market share. Coupled with a decline in national smoking prevalence, the result of Thailand\u27s stringent tobacco control agenda, the TTM now accounts for a diminishing share of a contracting market. In response, the monopoly has looked to regional trade liberalisation, and proximity to markets with some of the world\u27s highest smoking rates to expand its operations. Expansion strategies have gone largely unrealised however, and the TTM effectively remains a domestic operation. Using TTM publications, market and trade reports, industry publications, tobacco industry documents and other resources, this paper analyses TTM expansion strategies, and the limited extent to which they have been achieved. This inability to expand its operations has left the monopoly potentially vulnerable to global strategies of its transnational competitors. This article is part of the special issue \u27The Emergence of Asian Tobacco Companies: Implications for Global Health Governance\u27