Response to zinc deficiency of two rice lines with contrasting tolerance is determined by root growth maintenance and organic acid exudation rates, and not by zinc-transporter activity

Zinc (Zn)-deficient soils constrain rice (Oryza sativa) production and cause Zn malnutrition. The identification of Zn-deficiency-tolerant rice lines indicates that breeding might overcome these constraints. Here, we seek to identify processes underlying Zn-deficiency tolerance in rice at the physiological and transcriptional levels. A Zn-deficiency-tolerant line RIL46 acquires Zn more efficiently and produces more biomass than its nontolerant maternal line (IR74) at low Zn(ext) under field conditions. We tested if this was the result of increased expression of Zn(2+) transporters; increased root exudation of deoxymugineic acid (DMA) or low-molecular-weight organic acids (LMWOAs); and/or increased root production. Experiments were performed in field and controlled environment conditions. There was little genotypic variation in transcript abundance of Zn-responsive root Zn(2+)-transporters between the RIL46 and IR74. However, root exudation of DMA and LMWOA was greater in RIL46, coinciding with increased root expression of putative ligand-efflux genes. Adventitious root production was maintained in RIL46 at low Zn(ext), correlating with altered expression of root-specific auxin-responsive genes. Zinc-deficiency tolerance in RIL46 is most likely the result of maintenance of root growth, increased efflux of Zn ligands, and increased uptake of Zn-ligand complexes at low Zn(ext); these traits are potential breeding targets.

Gallium-sulphide supertetrahedral clusters as building blocks of covalent organic-inorganic networks

The synthesis and characterisation of novel covalent organic-inorganic architectures containing organically-functionalised supertetrahedra is described. The structures of these unique materials consist of one-dimensional zigzag chains or of honeycomb-type layers, in which gallium-sulfide supertetrahedral clusters and dipyridyl ligands alternate.

Privatisation, empowerment and accountability: What are the policy implications for establishing effective farmer organisations?

Weak institutional development and information flows have constrained the extent to which the small-holder farming sector in developing countries can significantly drive growth and poverty reduction. Thisis despite widely implemented economic liberalisation policies focussing on market efficiency. Farmerorganisations are viewed as a potential means of addressing public and private institutional failure but thishas frequently been limited by inequalities in access to power and information. This article investigatestwo issues that have received little research attention to date: what role downward accountability plays inenabling farmer organisations to improve services and markets, and what influences the extent to whichdownward accountability is achieved. Kenya Tea Development Agency (KTDA), one of the largest farmerorganisations in the world (>400,000 farmers) is examined alongside wider literature. Mixed methodswere used including key informant interviews, and eight months of participant observation followedby a questionnaire survey. The article concludes that without effective downward accountability farmerorganisations can become characterised by institutions and mechanisms that favour elites, restrictedweak coordination and regulation, and manipulated information flows. This in turn reduces individuals’incentives to invest. If farmer organisations are to realise their potential as a means of enabling the small-holder sector to significantly contribute to economic growth and poverty reduction, policy and researchneeds to address key factors which influence accountability including: how to ensure initial processes information of farmer organisations establish appropriate structures and rules; strong state regulation toenhance corporate accountability; transparent information provision regarding actions of farmer organi-sation leaders; and the role independent non-government organisations can play. Consequently attentionneeds to focus on developing means of legitimising rights, building poor people’s capacity to challengeexclusion, and moving from rights to obligations regarding information provision.

The impact of climate change on the treatability of dissolved organic matter (DOM) in upland water supplies: A UK perspective

Climate change in the UK is expected to cause increases in temperatures, altered precipitation patterns and more frequent and extreme weather events. In this review we discuss climate effects on dissolved organic matter (DOM), how altered DOM and water physico-chemical properties will affect treatment processes and assess the utility of techniques used to remove DOM and monitor water quality. A critical analysis of the literature has been undertaken with a focus on catchment drivers of DOM character, removal of DOM via coagulation and the formation of disinfectant by-products (DBPs). We suggest that: (1) upland catchments recovering from acidification will continue to produce more DOM with a greater hydrophobic fraction as solubility controls decrease; (2) greater seasonality in DOM export is likely in future due to altered precipitation patterns; (3) changes in species diversity and water properties could encourage algal blooms; and (4) that land management and vegetative changes may have significant effects on DOM export and treatability but require further research. Increases in DBPs may occur where catchments have high influence from peatlands or where algal blooms become an issue. To increase resilience to variable DOM quantity and character we suggest that one or more of the following steps are undertaken at the treatment works: a) ‘enhanced coagulation’ optimised for DOM removal; b) switching from aluminium to ferric coagulants and/or incorporating coagulant aids; c) use of magnetic ion-exchange (MIEX) pre-coagulation; and d) activated carbon filtration post-coagulation. Fluorescence and UV absorbance techniques are highlighted as potential methods for low-cost, rapid on-line process optimisation to improve DOM removal and minimise DBPs.

Substitutional and orientational disorder in organic crystals: a symmetry-adapted ensemble model

Modelling of disorder in organic crystals is highly desirable since it would allow thermodynamic stabilities and other disorder-sensitive properties to be estimated for such systems. Two disordered organic molecular systems are modeled using a symmetry-adapted ensemble approach, in which the disordered system is treated as an ensemble of the configurations of a supercell with respect to substitution of one disorder component for another. Computation time is kept manageable by performing calculations only on the symmetrically inequivalent configurations. Calculations are presented on a substitutionally disordered system, the dichloro/dibromobenzene solid solution, and on an orientationally disordered system, eniluracil, and the resultant free energies, disorder patterns, and system properties are discussed. The results are found to be in agreement with experiment following manual removal of physically implausible configurations from ensemble averages, highlighting the dangers of a completely automated approach to organic crystal thermodynamics which ignores the barriers to equilibration once the crystal has been formed.

The research productivity of the AIB Farmer Award finalists

Purpose – This paper aims to analyze the research productivity and impact of the finalists of the AIB best dissertation award, now titled the Buckley and Casson Award, but from 1987 to 2012 the Farmer Award. Specifically, this paper examines whether there is a relationship between winning the best dissertation award and subsequent publication productivity and impact. Relationships between academic institution and institutional geographic location and finalists are also examined. Design/methodology/approach – The paper examines 25 years of citation counts and the number of publications in Google Scholar of Farmer Award winners and finalists of the AIB best dissertation award from inception in 1987 to 2009, with cited publications as a measure of productivity and citations as a measure of impact. Top performers in productivity and impact are identified, and the averages of winners and non-winners are analyzed in aggregate, over time and per year. Data on finalists' institution and geographic location of institution are analyzed to describe the importance of location and institution to the award. Findings – It is found that the overall average citations of the winners of the award is less than that of the non-winners, and that in the large majority of years the non-winners have an average citation count higher than that of the winners. However, taking averages in five year increments shows more mixed results, with non-winners performing better in two periods and winners performing better in two periods, with the remaining period being split as to research productivity and impact. Originality/value – Aggarwal et al. in this journal summarized a variety of data on Farmer Award finalists from the 1990s to gain insights on institutions represented by finalists, the publication record of finalists, and content of dissertations, among other characteristics. This paper updates some of the insights from that paper by examining data on award winners from 1987 to 2013, and adds further insight by examining for the first time cited publications and citation counts winners and non-winners for the same period excluding the last two years.

Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent

Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.

Synthesis and characterization of inorganic-organic hybrid gallium selenides

Two semiconducting hybrid gallium selenides, [Ga6Se9(C6H14N2)4][H2O] (1) and [C6H14N2][Ga4Se6(C6H14N2)2] (2), were prepared using a solvothermal method in the pres-ence of 1,2-diaminocyclohexane (1,2-DACH). Both materials consist of neutral inorganic layers, in which 1,2-DACH is co-valently bonded to gallium. In (1), the organic amine acts as a monodentate and a bidentate ligand, while in (2) bidentate and uncoordinated 1,2-DACH molecules coexist.

Simulated climate change impact on summer dissolved organic carbon release from peat and surface vegetation: implications for drinking water treatment

Uncertainty regarding changes in dissolved organic carbon (DOC) quantity and quality has created interest in managing peatlands for their ecosystem services such as drinking water provision. The evidence base for such interventions is, however, sometimes contradictory. We performed a laboratory climate manipulation using a factorial design on two dominant peatland vegetation types (Calluna vulgaris and Sphagnum Spp.) and a peat soil collected from a drinking water catchment in Exmoor National Park, UK. Temperature and rainfall were set to represent baseline and future conditions under the UKCP09 2080s high emissions scenario for July and August. DOC leachate then underwent standard water treatment of coagulation/flocculation before chlorination. C. vulgaris leached more DOC than Sphagnum Spp. (7.17 versus 3.00 mg g−1) with higher specific ultraviolet (SUVA) values and a greater sensitivity to climate, leaching more DOC under simulated future conditions. The peat soil leached less DOC (0.37 mg g−1) than the vegetation and was less sensitive to climate. Differences in coagulation removal efficiency between the DOC sources appears to be driven by relative solubilisation of protein-like DOC, observed through the fluorescence peak C/T. Post-coagulation only differences between vegetation types were detected for the regulated disinfection by-products (DBPs), suggesting climate change influence at this scale can be removed via coagulation. Our results suggest current biodiversity restoration programmes to encourage Sphagnum Spp. will result in lower DOC concentrations and SUVA values, particularly with warmer and drier summers.

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.

Land use and climate change impacts on soil organic carbon stocks in semi-arid Spain

Purpose The sensitivity of soil organic carbon to global change drivers, according to the depth profile, is receiving increasing attention because of its importance in the global carbon cycle and its potential feedback to climate change. A better knowledge of the vertical distribution of SOC and its controlling factors—the aim of this study—will help scientists predict the consequences of global change. Materials and methods The study area was the Murcia Province (S.E. Spain) under semiarid Mediterranean conditions. The database used consists of 312 soil profiles collected in a systematic grid, each 12 km2 covering a total area of 11,004 km2. Statistical analysis to study the relationships between SOC concentration and control factors in different soil use scenarios was conducted at fixed depths of 0–20, 20–40, 40–60, and 60–100 cm. Results and discussion SOC concentration in the top 40 cm ranged between 6.1 and 31.5 g kg−1, with significant differences according to land use, soil type and lithology, while below this depth, no differences were observed (SOC concentration 2.1–6.8 g kg−1). The ANOVA showed that land use was the most important factor controlling SOC concentration in the 0–40 cm depth. Significant differences were found in the relative importance of environmental and textural factors according to land use and soil depth. In forestland, mean annual precipitation and texture were the main predictors of SOC, while in cropland and shrubland, the main predictors were mean annual temperature and lithology. Total SOC stored in the top 1 m in the region was about 79 Tg with a low mean density of 7.18 kg Cm−3. The vertical distribution of SOC was shallower in forestland and deeper in cropland. A reduction in rainfall would lead to SOC decrease in forestland and shrubland, and an increase of mean annual temperature would adversely affect SOC in croplands and shrubland. With increasing depth, the relative importance of climatic factors decreases and texture becomes more important in controlling SOC in all land uses. Conclusions Due to climate change, impacts will be much greater in surface SOC, the strategies for C sequestration should be focused on subsoil sequestration, which was hindered in forestland due to bedrock limitations to soil depth. In these conditions, sequestration in cropland through appropriate management practices is recommended.

Assessment of plant uptake models used in exposure assessment tools for soils contaminated with organic pollutants

The aim of this study was to evaluate and improve the accuracy of plant uptake models for neutral hydrophobic organic pollutants (1 < logKOW < 9, −8 < logKAW < 0) used in regulatory exposure assessment tools, using uncertainty and sensitivity analyses. The models considered were RAIDAR, EUSES, CSOIL, CLEA, and CalTOX. In this research, CSOIL demonstrated the best performance of all five exposure assessment tools for root uptake from polluted soil in comparison with observed data, but no model predicted shoot uptake well. Recalibration of the transpiration and volatilisation parameters improved the performance of CSOIL and CLEA. The dominant pathway for shoot uptake simulated differed according to the properties of the chemical under consideration; those with a higher air–water partition coefficient were transported into shoots via the soil-air-plant pathway, while chemicals with a lower octanol–water partition coefficient and air–water partition coefficient were transported via the root. The soil organic carbon content was a particularly sensitive parameter in each model and using a site specific value improved model performance.

The AeroCom evaluation and intercomparison of organic aerosol in global models

This paper evaluates the current status of global modeling of the organic aerosol (OA) in the troposphere and analyzes the differences between models as well as between models and observations. Thirty-one global chemistry transport models (CTMs) and general circulation models (GCMs) have participated in this intercomparison, in the framework of AeroCom phase II. The simulation of OA varies greatly between models in terms of the magnitude of primary emissions, secondary OA (SOA) formation, the number of OA species used (2 to 62), the complexity of OA parameterizations (gas-particle partitioning, chemical aging, multiphase chemistry, aerosol microphysics), and the OA physical, chemical and optical properties. The diversity of the global OA simulation results has increased since earlier AeroCom experiments, mainly due to the increasing complexity of the SOA parameterization in models, and the implementation of new, highly uncertain, OA sources. Diversity of over one order of magnitude exists in the modeled vertical distribution of OA concentrations that deserves a dedicated future study. Furthermore, although the OA / OC ratio depends on OA sources and atmospheric processing, and is important for model evaluation against OA and OC observations, it is resolved only by a few global models. The median global primary OA (POA) source strength is 56 Tg a−1 (range 34–144 Tg a−1) and the median SOA source strength (natural and anthropogenic) is 19 Tg a−1 (range 13–121 Tg a−1). Among the models that take into account the semi-volatile SOA nature, the median source is calculated to be 51 Tg a−1 (range 16–121 Tg a−1), much larger than the median value of the models that calculate SOA in a more simplistic way (19 Tg a−1; range 13–20 Tg a−1, with one model at 37 Tg a−1). The median atmospheric burden of OA is 1.4 Tg (24 models in the range of 0.6–2.0 Tg and 4 between 2.0 and 3.8 Tg), with a median OA lifetime of 5.4 days (range 3.8–9.6 days). In models that reported both OA and sulfate burdens, the median value of the OA/sulfate burden ratio is calculated to be 0.77; 13 models calculate a ratio lower than 1, and 9 models higher than 1. For 26 models that reported OA deposition fluxes, the median wet removal is 70 Tg a−1 (range 28–209 Tg a−1), which is on average 85% of the total OA deposition. Fine aerosol organic carbon (OC) and OA observations from continuous monitoring networks and individual field campaigns have been used for model evaluation. At urban locations, the model–observation comparison indicates missing knowledge on anthropogenic OA sources, both strength and seasonality. The combined model–measurements analysis suggests the existence of increased OA levels during summer due to biogenic SOA formation over large areas of the USA that can be of the same order of magnitude as the POA, even at urban locations, and contribute to the measured urban seasonal pattern. Global models are able to simulate the high secondary character of OA observed in the atmosphere as a result of SOA formation and POA aging, although the amount of OA present in the atmosphere remains largely underestimated, with a mean normalized bias (MNB) equal to −0.62 (−0.51) based on the comparison against OC (OA) urban data of all models at the surface, −0.15 (+0.51) when compared with remote measurements, and −0.30 for marine locations with OC data. The mean temporal correlations across all stations are low when compared with OC (OA) measurements: 0.47 (0.52) for urban stations, 0.39 (0.37) for remote stations, and 0.25 for marine stations with OC data. The combination of high (negative) MNB and higher correlation at urban stations when compared with the low MNB and lower correlation at remote sites suggests that knowledge about the processes that govern aerosol processing, transport and removal, on top of their sources, is important at the remote stations. There is no clear change in model skill with increasing model complexity with regard to OC or OA mass concentration. However, the complexity is needed in models in order to distinguish between anthropogenic and natural OA as needed for climate mitigation, and to calculate the impact of OA on climate accurately.

Effect of milk type and processing on iodine concentration of organic and conventional winter milk at retail: implications for nutrition

Milk is the largest source of iodine in UK diets and an earlier study showed that organic summer milk had significantly lower iodine concentration than conventional milk. There are no comparable studies with winter milk or the effect of milk fat class or heat processing method. Two retail studies with winter milk are reported. Study 1 showed no effect of fat class but organic milk was 32.2% lower in iodine than conventional milk (404 vs. 595 μg/L; P < 0.001). Study 2 found no difference between conventional and Channel Island milk but organic milk contained 35.5% less iodine than conventional milk (474 vs. 306 μg/L; P < 0.001). UHT and branded organic milk also had lower iodine concentrations than conventional milk (331 μg/L; P < 0.001 and 268 μg/L: P < 0.0001 respectively). The results indicate that replacement of conventional milk by organic or UHT milk will increase the risk of sub-optimal iodine status especially for pregnant/lactating women.