Modeling lightning-NOx chemistry on a sub-grid scale in a global chemical transport model

For the first time, a plume-in-grid approach is implemented in a chemical transport model (CTM) to parameterize the effects of the nonlinear reactions occurring within high concentrated NO_<i>x</i> plumes from lightning NO_<i>x</i> emissions (LNO_<i>x</i>) in the upper troposphere. It is characterized by a set of parameters including the plume lifetime, the effective reaction rate constant related to NO_<i>x</i>–O₃ chemical interactions, and the fractions of NO_<i>x</i> conversion into HNO₃ within the plume. Parameter estimates were made using the Dynamical Simple Model of Atmospheric Chemical Complexity (DSMACC) box model, simple plume dispersion simulations, and the 3-D Meso-NH (non-hydrostatic mesoscale atmospheric model). In order to assess the impact of the LNO_<i>x</i> plume approach on the NO_<i>x</i> and O₃ distributions on a large scale, simulations for the year 2006 were performed using the GEOS-Chem global model with a horizontal resolution of 2° × 2.5°. The implementation of the LNO_<i>x</i> parameterization implies an NO_<i>x</i> and O₃ decrease on a large scale over the region characterized by a strong lightning activity (up to 25 and 8 %, respectively, over central Africa in July) and a relative increase downwind of LNO_<i>x</i> emissions (up to 18 and 2 % for NO_<i>x</i> and O₃, respectively, in July). The calculated variability in NO_<i>x</i> and O₃ mixing ratios around the mean value according to the known uncertainties in the parameter estimates is at a maximum over continental tropical regions with ΔNO_<i>x</i> [−33.1, +29.7] ppt and ΔO₃ [−1.56, +2.16] ppb, in January, and ΔNO_<i>x</i> [−14.3, +21] ppt and ΔO₃ [−1.18, +1.93] ppb, in July, mainly depending on the determination of the diffusion properties of the atmosphere and the initial NO mixing ratio injected by lightning. This approach allows us (i) to reproduce a more realistic lightning NO_<i>x</i> chemistry leading to better NO_<i>x</i> and O₃ distributions on the large scale and (ii) to focus on other improvements to reduce remaining uncertainties from processes related to NO_<i>x</i> chemistry in CTM

Acceleration of global N₂O emissions seen from two decades of atmospheric inversion

Nitrous oxide (N2O) is the third most important long-lived GHG and an important stratospheric ozone depleting substance. Agricultural practices and the use of N-fertilizers have greatly enhanced emissions of N2O. Here, we present estimates of N2O emissions determined from three global atmospheric inversion frameworks during the period 1998–2016. We find that global N2O emissions increased substantially from 2009 and at a faster rate than estimated by the IPCC emission factor approach. The regions of East Asia and South America made the largest contributions to the global increase. From the inversion-based emissions, we estimate a global emission factor of 2.3 ± 0.6%, which is significantly larger than the IPCC Tier-1 default for combined direct and indirect emissions of 1.375%. The larger emission factor and accelerating emission increase found from the inversions suggest that N2O emission may have a nonlinear response at global and regional scales with high levels of N-input

High toxicity and specificity of the saponin 3-GlcA-28-AraRhaxyl-medicagenate, from Medicago truncatula seeds, for Sitophilus oryzae

<p>Abstract</p> <p>Background</p> <p>Because of the increasingly concern of consumers and public policy about problems for environment and for public health due to chemical pesticides, the search for molecules more safe is currently of great importance. Particularly, plants are able to fight the pathogens as insects, bacteria or fungi; so that plants could represent a valuable source of new molecules.</p> <p>Results</p> <p>It was observed that <it>Medicago truncatul</it>a seed flour displayed a strong toxic activity towards the adults of the rice weevil <it>Sitophilus oryzae</it> (Coleoptera), a major pest of stored cereals. The molecule responsible for toxicity was purified, by solvent extraction and HPLC, and identified as a saponin, namely 3-GlcA-28-AraRhaxyl-medicagenate. Saponins are detergents, and the CMC of this molecule was found to be 0.65 mg per mL. Neither the worm <it>Caenorhabditis elegans</it> nor the bacteria <it>E. coli</it> were found to be sensitive to this saponin, but growth of the yeast <it>Saccharomyces cerevisiae</it> was inhibited at concentrations higher than 100 μg per mL. The purified molecule is toxic for the adults of the rice weevils at concentrations down to 100 μg per g of food, but this does not apply to the others insects tested, including the coleopteran <it>Tribolium castaneum</it> and the Sf9 insect cultured cells.</p> <p>Conclusions</p> <p>This specificity for the weevil led us to investigate this saponin potential for pest control and to propose the hypothesis that this saponin has a specific mode of action, rather than acting <it>via</it> its non-specific detergent properties.</p

A folded and functional synthetic PA1b, an interlocked entomotoxic miniprotein

1-ACL (articles avec comité de lecture)PA1b (Pea Albumin 1, subunit b) is a hydrophobic, 37-amino acid niiniprotein isolated from pea seeds (Pivum sativum), crosslinked by three interlocked disulfide bridges, signature of the ICK (inhibitory cystine-knot) family. It acts as an entomotoxic factor against major insect pests in stored crops and vegetables, making it a promising bioinsecticide. Here we report an efficient and simple protocol for the production of large quantities of highly pure, biologically active synthetic PA1b. The features of PA1b oxidative refolding revealed the off-pathway products and competitive aggregation processes. The efficiency of the oxidative folding can be significantly improved by using hydrophobic alcoholic cosolvents and decreasing the temperature. The homogeneity of the synthetic oxidized PA1b was established by reversed-phase HPLC. The correct pairing of the three disulfide bridges, as well as the three-dimensional structure of synthetic PA1b was assessed by NMR. Synthetic PA1b binds to rnicrosomal proteins from Sitophilus oryzae with a Kd of 8 nM, a figure quite similar to that determined for PA1b extracted from its natural source. Moreover, the synthetic miniprotein was as potent as the extracted one towards the sensitive strains of weevils. Our findings will open the way to the production of PA1b analogues by chemical means to an in-depth understanding of the PA1b mechanism of action

Minimising haemodynamic lability during changeover of syringes infusing norepinephrine in adult critical care patients: a multicentre randomised controlled trial.

Arterial pressure lability is common during the process of replacing syringes used for norepinephrine infusions in critically ill patients. It is unclear if there is an optimal approach to minimise arterial pressure instability during this procedures. We investigated whether 'double pumping' changeover (DPC) or automated changeover (AC) reduced blood pressure lability in critically ill adults compared with quick syringe changeover (QC). Patients requiring a norepinephrine infusion syringe change were randomised in a non-blinded trial undertaken in six ICUs. Randomisation was minimised by norepinephrine flow rate at inclusion and centre. The primary outcome was the frequency of increased/decreased mean arterial pressure (defined by &lt;/&gt;15 mm Hg from baseline measurements) within 15 min of switching the syringe compared with QC. Patients (mean age: 64 (range:18-88)) yr were randomly assigned to QC (n=95), DPC (n=95), or AC (n=96). Increased MAP was the commonest consequence of syringe changeovers. MAP variability was most frequent after DPC (89/224 changeovers; 39.7%) compared with 57/223 (25.6%) changeovers after quick syringe switch and 46/181 (25.4%) in patients randomised to receive automated changeover (P=0.001). Fewer events occurred with QC compared with DPC (P=0.002). Sensitivity analysis based on mixed models showed that performing several changeovers on a single patient had no impact. Both type of changeover and norepinephrine dose before syringe changeover were independently associated with MAP variations &gt;15 mm Hg. Quick changeover of norepinephrine syringes was associated with less blood pressure lability compared with DPC. The prevalence of MAP variations was the same between AC and QC. NCT02304939

Ligand specificity of a high-affinity binding site for lipo-chitooligosaccharidic Nod factors in Medicago cell suspension cultures

Rhizobial lipo-chitooligosaccharides (LCOs) are signaling molecules involved in host-range recognition for the establishment of the symbiosis with leguminous plants. The major LCO of Rhizobium meliloti, the symbiont of Medicago plants contains four or five N-acetylglucosamines, O-acetylated and N-acylated with a C16:2 fatty acid on the terminal nonreducing sugar and O-sulfated on the reducing sugar. In this paper, the ligand specificity of a high-affinity binding site (Nod factor binding site 2 or NFBS2), enriched in a plasma membrane-enriched fraction of Medicago cell suspension cultures, is reported. By using chemically synthesized LCOs, the role of structural elements, important for symbiotic activities, as recognition motifs for NFBS2 was determined. The results show that the substitutions on the nonreducing sugar of the LCOs (the O-acetate group, the fatty acid, and the hydroxyl group on the C(4) of the sugar) are determinants for high-affinity binding to NFBS2. In contrast, the sulfate group, which is necessary for all biological activities on Medicago, is not discriminated by NFBS2. However, the reducing sugar of the LCO seems to interact with NFBS2, because ligand binding is affected by the reduction of the free anomeric carbon and depends on the number of N-acetyl glucosamine residues. These results suggest that the recognition of the LCOs by NFBS2 is mediated by structural elements in both the lipid and oligosaccharidic moities, but not by the sulfate group

Lightning NOx influence on large scale NOy and O3 plumes observed over the northern mid-latitudes

This paper describes the NOy plumes originating from lightning emissions based on 4 yr (2001–2005) of MOZAIC measurements in the upper troposphere of the northern mid-latitudes, together with ground- and space-based observations of lightning flashes and clouds. This analysis is primarily for the North Atlantic region where the MOZAIC flights are the most frequent and for which the measurements are well representative in space and time. The study investigates the influence of lightning NOx (LNOx) emissions on large-scale (300–2000 km) plumes (LSPs) of NOy. One hundred and twenty seven LSPs (6% of the total MOZAIC NOy dataset) have been attributed to LNOx emissions. Most of these LSPs were recorded over North America and the Atlantic mainly in spring and summer during the maximum lightning activity occurrence. The majority of the LSPs (74%) is related to warm conveyor belts and extra-tropical cyclones originating from North America and entering the intercontinental transport pathway between North America and Europe, leading to a negative (positive) west to east NOy (O3) zonal gradient with −0.4 (+18) ppbv difference during spring and −0.6 (+14) ppbv difference in summer. The NOy zonal gradient can correspond to the mixing of the plume with the background air. On the other hand, the O3 gradient is associated with both mixing of background air and with photochemical production during transport. Such transatlantic LSPs may have a potential impact on the European pollution. The remaining sampled LSPs are related to mesoscale convection over Western Europe and the Mediterranean Sea (18%) and to tropical convection (8%)