Substrate-induced bandgap in graphene on hexagonal boron nitride

We determine the electronic structure of a graphene sheet on top of a lattice-matched hexagonal boron nitride (h-BN) substrate using ab initio density functional calculations. The most stable configuration has one carbon atom on top of a boron atom, the other centered above a BN ring. The resulting inequivalence of the two carbon sites leads to the opening of a gap of 53 meV at the Dirac points of graphene and to finite masses for the Dirac fermions. Alternative orientations of the graphene sheet on the BN substrate generate similar band gaps and masses. The band gap induced by the BN surface can greatly improve room temperature pinch-off characteristics of graphene-based field effect transistors.Comment: 5 pages, 4 figures, Phys. Rev. B, in pres

Decomposition of Algebraic Functions

AbstractFunctional decomposition—whether a functionf(x) can be written as a composition of functionsg(h(x)) in a non-trivial way—is an important primitive in symbolic computation systems. The problem of univariate polynomial decomposition was shown to have an efficient solution by Kozen and Landau (1989). Dickerson (1987) and Gathen (1990a) gave algorithms for certain multivariate cases. Zippel (1991) showed how to decompose rational functions. In this paper, we address the issue of decomposition of algebraic functions. We show that the problem is related to univariate resultants in algebraic function fields, and in fact can be reformulated as a problem ofresultant decomposition. We characterize all decompositions of a given algebraic function up to isomorphism, and give an exponential time algorithm for finding a non-trivial one if it exists. The algorithm involves genus calculations and constructing transcendental generators of fields of genus zero

Ethoprophos fate on soil–water interface and effects on non-target terrestrial and aquatic biota under Mediterranean crop-based scenarios

The present study aimed to assess the environmental fate of the insecticide and nematicide ethoprophos in the soil–water interface following the pesticide application in simulated maize and potato crops under Mediterranean agricultural conditions, particularly of irrigation. Focus was given to the soil–water transfer pathways (leaching and runoff), to the pesticide transport in soil between pesticide application (crop row) and non-application areas (between crop rows), as well as to toxic effects of the various matrices on terrestrial and aquatic biota. A semi-field methodology mimicking a “worst-case” ethoprophos application (twice the recommended dosage for maize and potato crops: 100% concentration v/v) in agricultural field situations was used, in order to mimic a possible misuse by the farmer under realistic conditions. A rainfall was simulated under a slope of 20° for both crop-based scenarios. Soil and water samples were collected for the analysis of pesticide residues. Ecotoxicity of soil and aquatic samples was assessed by performing lethal and sublethal bioassays with organisms from different trophic levels: the collembolan Folsomia candida, the earthworm Eisenia andrei and the cladoceran Daphnia magna. Although the majority of ethoprophos sorbed to the soil application area, pesticide concentrations were detected in all water matrices illustrating pesticide transfer pathways of water contamination between environmental compartments. Leaching to groundwater proved to be an important transfer pathway of ethoprophos under both crop-based scenarios, as it resulted in high pesticide concentration in leachates from Maize (130 µg L−1) and Potato (630 µg L−1) crop scenarios, respectively. Ethoprophos application at the Potato crop scenario caused more toxic effects on terrestrial and aquatic biota than at the Maize scenario at the recommended dosage and lower concentrations. In both crop-based scenarios, ethoprophos moved with the irrigation water flow to the soil between the crop rows where no pesticide was applied, causing toxic effects on terrestrial organisms. The two simulated agricultural crop-based scenarios had the merit to illustrate the importance of transfer pathways of pesticides from soil to groundwater through leaching and from crop rows to the surrounding soil areas in a soil–water interface environment, which is representative for irrigated agricultural crops under Mediterranean conditions.This studywaspartlysponsoredbytheEuropeanFundfor Economic andRegionalDevelopment(FEDER)throughthePro- gram OperationalFactorsofCompetitiveness(COMPETE)and National FundsthroughthePortugueseFoundationofScience and Technology(Ph.D.granttoSaraLeitão – SFRH/BD/42306/2007, Ciência 2007 – POPH andQREN,andTerbAzineBiorem – PTDC/ AAC-AMB/111317/2009)

Ecological impacts of time-variable exposure regimes to the fungicide azoxystrobin on freshwater communities in outdoor microcosms

This paper evaluates the effects of different time-varying exposure patterns of the strobilurin fungicide azoxystrobin on freshwater microsocosm communities. These exposure patterns included two treatments with a similar peak but different time-weighted average (TWA) concentrations, and two treatments with similar TWA but different peak concentrations. The experiment was carried out in outdoor microcosms under four different exposure regimes; (1) a continuous application treatment of 10 μg/L (CAT10) for 42 days (2), a continuous application treatment of 33 μg/L (CAT33) for 42 days (3), a single application treatment of 33 μg/L (SAT33) and (4) a four application treatment of 16 μg/L (FAT16), with a time interval of 10 days. Mean measured 42-d TWA concentrations in the different treatments were 9.4 μg/L (CAT10), 32.8 μg/L (CAT33), 14.9 μg/L (SAT33) and 14.7 μg/L (FAT16). Multivariate analyses demonstrated significant changes in zooplankton community structure in all but the CAT10 treated microcosms relative to that of controls. The largest adverse effects were reported for zooplankton taxa belonging to Copepoda and Cladocera. By the end of the experimental period (day 42 after treatment), community effects were of similar magnitude for the pulsed treatment regimes, although the magnitude of the initial effect was larger in the SAT33 treatment. This indicates that for long-term effects the TWA is more important for most zooplankton species in the test system than the peak concentration. Azoxystrobin only slightly affected some species of the macroinvertebrate, phytoplankton and macrophyte assemblages. The overall no observed ecologically adverse effect concentrations (NOEAEC) in this study was 10 µg/L

Potential impact of chemical stress on freshwater invertebrates : A sensitivity assessment on continental and national scale based on distribution patterns, biological traits, and relatedness.

Current chemical risk assessment approaches rely on a standard suite of test species to assess toxicity to environmental species. Assessment factors are used to extrapolate from single species to communities and ecosystem effects. This approach is pragmatic, but lacks resolution in biological and environmental parameters. Novel modelling approaches can help improve the biological resolution of assessments by using mechanistic information to identify priority species and priority regions that are potentially most impacted by chemical stressors. In this study we developed predictive sensitivity models by combining species-specific information on acute chemical sensitivity (LC50 and EC50), traits, and taxonomic relatedness. These models were applied at two spatial scales to reveal spatial differences in the sensitivity of species assemblages towards two chemical modes of action (MOA): narcosis and acetylcholinesterase (AChE) inhibition. We found that on a relative scale, 46% and 33% of European species were ranked as more sensitive towards narcosis and AChE inhibition, respectively. These more sensitive species were distributed with higher occurrences in the south and north-eastern regions, reflecting known continental patterns of endemic macroinvertebrate biodiversity. We found contradicting sensitivity patterns depending on the MOA for UK scenarios, with more species displaying relative sensitivity to narcotic MOA in north and north-western regions, and more species with relative sensitivity to AChE inhibition MOA in south and south-western regions. Overall, we identified hotspots of species sensitive to chemical stressors at two spatial scales, and discuss data gaps and crucial technological advances required for the successful application of the proposed methodology to invertebrate scenarios, which remain underrepresented in global conservation priorities.</p

Effects of the Veterinary Pharmaceutical Ivermectin in Indoor Aquatic Microcosms

The effects of the parasiticide ivermectin were assessed in plankton-dominated indoor microcosms. Ivermectin was applied once at concentrations of 30, 100, 300, 1000, 3000, and 10,000 ng/l. The half-life (dissipation time 50%; DT50) of ivermectin in the water phase ranged from 1.1 to 8.3 days. The lowest NOECcommunity that could be derived on an isolated sampling from the microcosm study by means of multivariate techniques was 100 ng/l. The most sensitive species in the microcosm study were the cladocerans Ceriodaphnia sp. (no observed effect concentration, NOEC = 30 ng/l) and Chydorus sphaericus (NOEC = 100 ng/l). The amphipod Gammarus pulex was less sensitive to ivermectin, showing consistent statistically significant reductions at the 1000-ng/l treatment level. Copepoda taxa decreased directly after application of ivermectin in the highest treatment but had already recovered at day 20 posttreatment. Indirect effects (e.g., increase of rotifers, increased primary production) were observed at the highest treatment level starting only on day 13 of the exposure phase. Cladocera showed the highest sensitivity to ivermectin in both standard laboratory toxicity tests as well as in the microcosm study. This study demonstrates that simple plankton-dominated test systems for assessing the effects of ivermectin can produce results similar to those obtained with large complex outdoor systems

Using a Bayesian Network Model to Predict Risk of Pesticides on Aquatic Community Endpoints in a Rice Field—A Southern European Case Study

Bayesian network (BN) models are increasingly used as tools to support probabilistic environmental risk assessments (ERAs), because they can better account for uncertainty compared with the simpler approaches commonly used in traditional ERA. We used BNs as metamodels to link various sources of information in a probabilistic framework, to predict the risk of pesticides to aquatic communities under given scenarios. The research focused on rice fields surrounding the Albufera Natural Park (Valencia, Spain), and considered three selected pesticides: acetamiprid (an insecticide), 2-methyl-4-chlorophenoxyacetic acid (MCPA; a herbicide), and azoxystrobin (a fungicide). The developed BN linked the inputs and outputs of two pesticide models: a process-based exposure model (Rice Water Quality [RICEWQ]), and a probabilistic effects model (Predicts the Ecological Risk of Pesticides [PERPEST]) using case-based reasoning with data from microcosm and mesocosm experiments. The model characterized risk at three levels in a hierarchy: biological endpoints (e.g., molluscs, zooplankton, insects, etc.), endpoint groups (plants, invertebrates, vertebrates, and community processes), and community. The pesticide risk to a biological endpoint was characterized as the probability of an effect for a given pesticide concentration interval. The risk to an endpoint group was calculated as the joint probability of effect on any of the endpoints in the group. Likewise, community-level risk was calculated as the joint probability of any of the endpoint groups being affected. This approach enabled comparison of risk to endpoint groups across different pesticide types. For example, in a scenario for the year 2050, the predicted risk of the insecticide to the community (40% probability of effect) was dominated by the risk to invertebrates (36% risk). In contrast, herbicide-related risk to the community (63%) resulted from risk to both plants (35%) and invertebrates (38%); the latter might represent (in the present study) indirect effects of toxicity through the food chain. This novel approach combines the quantification of spatial variability of exposure with probabilistic risk prediction for different components of aquatic ecosystems.publishedVersio

Pesticides decrease bacterial diversity and abundance of irrigated rice fields

Bacteria play an important role in soil ecosystems and their activities are crucial in nutrient composition and recycling. Pesticides are extensively used in agriculture to control pests and improve yield. However, increased use of pesticides on agricultural lands results in soil contamination, which could have adverse effect on its bacterial communities. Here, we investigated the effect of pesticides commonly used on irrigated rice fields on bacterial abundance and diversity. Irrigated soil samples collected from unexposed, pesticide‐exposed, and residual exposure areas were cultured under aerobic and anaerobic conditions. DNA was extracted and analysed by 16S rRNA sequencing. The results showed overall decrease in bacterial abundance and diversity in areas exposed to pesticides. Operational taxonomic units of the genera Enterobacter, Aeromonas, Comamonas, Stenotrophomonas, Bordetella, and Staphylococcus decreased in areas exposed to pesticides. Conversely, Domibacillus, Acinetobacter, Pseudomonas, and Bacillus increased in abundance in pesticide‐exposed areas. Simpson and Shannon diversity indices and canonical correspondence analysis demonstrated a decrease in bacterial diversity and composition in areas exposed to pesticides. These results suggest bacteria genera unaffected by pesticides that could be further evaluated to identify species for bioremediation. Moreover, there is a need for alternative ways of improving agricultural productivity and to educate farmers to adopt innovative integrated pest management strategies to reduce deleterious impacts of pesticides on soil ecosystems.</p