Global oceanic emission of ammonia: Constraints from seawater and atmospheric observations

Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia (NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NHx(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NHx(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.

Decadal reanalysis of biogeochemical indicators and fluxes in the North West European shelf-sea ecosystem

In this paper we present the first decadal reanalysis simulation of the biogeochemistry of the North West European shelf, along with a full evaluation of its skill and value. An error-characterized satellite product for chlorophyll was assimilated into a physical-biogeochemical model of the North East Atlantic, applying a localized Ensemble Kalman filter. The results showed that the reanalysis improved the model predictions of assimilated chlorophyll in 60% of the study region. Model validation metrics showed that the reanalysis had skill in matching a large dataset of in situ observations for ten ecosystem variables. Spearman rank correlations were significant and higher than 0.7 for physical-chemical variables (temperature, salinity, oxygen), ∼0.6 for chlorophyll and nutrients (phosphate, nitrate, silicate), and significant, though lower in value, for partial pressure of dissolved carbon dioxide (∼0.4). The reanalysis captured the magnitude of pH and ammonia observations, but not their variability. The value of the reanalysis for assessing environmental status and variability has been exemplified in two case studies. The first shows that between 340,000-380,000 km2 of shelf bottom waters were oxygen deficient potentially threatening bottom fishes and benthos. The second application confirmed that the shelf is a net sink of atmospheric carbon dioxide, but the total amount of uptake varies between 36-46 Tg C yr−1 at a 90% confidence level. These results indicate that the reanalysis output dataset can inform the management of the North West European shelf ecosystem, in relation to eutrophication, fishery, and variability of the carbon cycle.

Attribution of Atmospheric Sulfur Dioxide over the English Channel to Dimethylsulfide and Changing Ship Emissions

Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory(PPAO) near Plymouth, United Kingdom between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near the Plymouth Sound. New International Maritime Organization (IMO) regulation came into force in January 2015 to reduce sulfur emissions tenfold in Sulfur Emission Control Areas such as the English Channel. Our observations suggest a three-fold reduction from 2014 to 2015 in ship-emitted SO2 from that direction. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plum es show a high level of compliance to the IMO regulation (> 95 %) in both years. Dimethylsulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from ~ 1/3 in 2014 to ~ 1/2 in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

Detection and impacts of leakage from sub-seafloor deep geological carbon dioxide storage

Fossil fuel power generation and other industrial emissions of carbon dioxide are a threat to global climate1, yet many economies will remain reliant on these technologies for several decades2. Carbon dioxide capture and storage (CCS) in deep geological formations provides an effective option to remove these emissions from the climate system3. In many regions storage reservoirs are located offshore4, 5, over a kilometre or more below societally important shelf seas6. Therefore, concerns about the possibility of leakage7, 8 and potential environmental impacts, along with economics, have contributed to delaying development of operational CCS. Here we investigate the detectability and environmental impact of leakage from a controlled sub-seabed release of CO2. We show that the biological impact and footprint of this small leak analogue (<1 tonne CO2 d−1) is confined to a few tens of metres. Migration of CO2 through the shallow seabed is influenced by near-surface sediment structure, and by dissolution and re-precipitation of calcium carbonate naturally present in sediments. Results reported here advance the understanding of environmental sensitivity to leakage and identify appropriate monitoring strategies for full-scale carbon storage operations.

Ca2+- and volume-sensitive chloride currents are differentially regulated by agonists and store-operated Ca2+ entry.

Using patch-clamp and calcium imaging techniques, we characterized the effects of ATP and histamine on human keratinocytes. In the HaCaT cell line, both receptor agonists induced a transient elevation of [Ca2+]i in a Ca2+-free medium followed by a secondary [Ca2+]i rise upon Ca2+ readmission due to store-operated calcium entry (SOCE). In voltage-clamped cells, agonists activated two kinetically distinct currents, which showed differing voltage dependences and were identified as Ca2+-activated (ICl(Ca)) and volume-regulated (ICl, swell) chloride currents. NPPB and DIDS more efficiently inhibited ICl(Ca) and ICl, swell, respectively. Cell swelling caused by hypotonic solution invariably activated ICl, swell while regulatory volume decrease occurred in intact cells, as was found in flow cytometry experiments. The PLC inhibitor U-73122 blocked both agonist- and cell swelling–induced ICl, swell, while its inactive analogue U-73343 had no effect. ICl(Ca) could be activated by cytoplasmic calcium increase due to thapsigargin (TG)-induced SOCE as well as by buffering [Ca2+]i in the pipette solution at 500 nM. In contrast, ICl, swell could be directly activated by 1-oleoyl-2-acetyl-sn-glycerol (OAG), a cell-permeable DAG analogue, but neither by InsP3 infusion nor by the cytoplasmic calcium increase. PKC also had no role in its regulation. Agonists, OAG, and cell swelling induced ICl, swell in a nonadditive manner, suggesting their convergence on a common pathway. ICl, swell and ICl(Ca) showed only a limited overlap (i.e., simultaneous activation), although various maneuvers were able to induce these currents sequentially in the same cell. TG-induced SOCE strongly potentiated ICl(Ca), but abolished ICl, swell, thereby providing a clue for this paradox. Thus, we have established for the first time using a keratinocyte model that ICl, swell can be physiologically activated under isotonic conditions by receptors coupled to the phosphoinositide pathway. These results also suggest a novel function for SOCE, which can operate as a "selection" switch between closely localized channels.

Degradation of poly-L-lactide. Part2 : increased temperature accelerated degradation

Poly-L-lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioresorbable. The degradation of PLLA proceeds through hydrolysis of the ester linkages in the polymer's backbone; however, the time for the complete resorption of orthopaedic devices manufactured from PLLA is known to be in excess of five years in a normal physiological environment. To evaluate the degradation of PLLA in an accelerated time period, PLLA pellets were processed by compression moulding into tensile test specimens, prior to being sterilized by ethylene oxide gas (EtO) and degraded in a phosphate-buffered solution (PBS) at both 50°C and 70°C. On retrieval, at predetermined time intervals, procedures were used to evaluate the material's molecular weight, crystallinity, mechanical strength, and thermal properties. The results from this study suggest that at both 50°C and 70°C, degradation proceeds by a very similar mechanism to that observed at 37°C in vitro and in vivo. The degradation models developed also confirmed the dependence of mass loss, melting temperature, and glass transition temperature (Tg) on the polymer's molecular weight throughout degradation. Although increased temperature appears to be a suitable method for accelerating the degradation of PLLA, relative to its physiological degradation rate, concerns still remain over the validity of testing above the polymer's Tg and the significance of autocatalysis at increased temperatures.

Neutral and Charged 1-Butyl-3-methylimidazolium Triflate Clusters: Equilibrium Concentration in the Vapor Phase and Thermal Properties of Nanometric Droplets

Ground state energy, structure, and harmonic vibrational modes of 1-butyl-3-methylimidazolium triflate ([bmim][Tf]) clusters have been computed using an all-atom empirical potential model. Neutral and charged species have been considered up to a size (30 [bmim][Tf] pairs) well into the nanometric range. Free energy computations and thermodynamic modeling have been used to predict the equilibrium composition of the vapor phase as a function of temperature and density. The results point to a nonnegligible concentration of very small charged species at pressures (P ~ 0.01 Pa) and temperatures (T 600 K) at the boundary of the stability range of [bmim][Tf]. Thermal properties of nanometric neutral droplets have been investigated in the 0 T 700 K range. A near-continuous transition between a liquidlike phase at high T and a solidlike phase at low T takes place at T ~ 190 K in close correspondence with the bulk glass point Tg ~ 200 K. Solidification is accompanied by a transition in the dielectric properties of the droplet, giving rise to a small permanent dipole embedded into the solid cluster. The simulation results highlight the molecular precursors of several macroscopic properties and phenomena and point to the close competition of Coulomb and dispersion forces as their common origin.

Thermogravimetric evaluation of perennial ryegrass (Lolium perenne) for the prediction of in vitro dry matter digestibility

Thermogravimetry (TG) can be used for assessing the compositional differences in grasses that relate to dry matter digestibility (DMD) determined by pepsin-cellulase assay. This investigation developed regression models for predicting DMD of herbage grass during one growing season using TG results. The calibration samples were obtained from a field trial of eight cultivars and two breeding lines. The harvested materials from five cuts were analysed by TG to identify differences in the combustion patterns within the range of 30-600 degrees C. The discrete results including weight loss, peak height, area, temperature, widths and residue of three decomposition peaks were regressed against the measured DMD values of the calibration samples. Similarly, continuous weight loss results of the same samples were also utilised to generate DMD models. The r(2) for validation of the discrete and the best continuous models were 0.90 and 0.95, respectively, and the two calibrations were validated using independent samples from 24 plots from a trial carried out in 2004. The standard error for prediction of the 24 samples by the discrete model (4.14%) was higher than that by the continuous model (2.98%). This study has shown that DMD of grass could be predicted from the TG results. The benefit of thermal analysis is the ability to detect and show changes in composition of cell wall fractions of grasses during different cuts in a year.

Acylation of sulfonamines using silica grafted 1-butyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium ionic liquids as catalysts

Heterogeneous immobilized ionic liquid catalysts were prepared via grafting of 1,3-dimethyl-3-(3-triethoxysilylpropyl)-imidazolium tetrafluoroborate or bist{(trifluoromethyl)sulfonyl} imide ([NTf2](-)) on silica supports with different surfaces and pore size. In addition to the adsorption-desorption isotherms of nitrogen at -196C, the catalysts were characterized by TG-DTA, XPS, DRIFTS, DR-UV-vis, NMR, and XRD techniques. The catalytic behavior was checked in the acylation of three different sulfonamines: benzenesulfonamine, p-nitrobenzene-sulfonamine, and p-methoxybenzene-sulfonamine with acetic acid, acetic anhydride and maleic anhydride. These tests confirmed the acid Lewis properties of these catalysts. (c) 2007 Elsevier B.V. All rights reserved.

Association of gene expression with sequential proliferation, differentiation and tumor formation in murine skin

Differential gene expression in two established initiation and promotion skin carcinogenesis models during promotion and tumor formation was determined by microarray technology with the purpose of distinguishing the genes more associated with neoplastic transformation from those linked with proliferation and differentiation. The first model utilized dimethylbenz[a]anthracene initiation and 12-O-tetradecanoylphorbol 13-acetate (TPA) promotion in the FVB/N mouse, and the second TPA promotion of the Tg.Ac mouse, which is endogenously initiated by virtue of an activated Ha-ras transgene. Comparison of gene expression profiles across the two models identified genes whose altered expression was associated with papilloma formation rather than TPA-induced proliferation and differentiation. DMBA suppressed TPA-induced differentiation which allowed identification of those genes associated more specifically with differentiation rather than proliferation. EASE (Expression Analysis Systemic Explorer) indicated a correlation between muscle-associated genes and skin differentiation, whereas genes involved with protein biosynthesis were strongly correlated with proliferation. For verification the altered expression of selected genes were confirmed by RT-PCR; Carbonic anhydrase 2, Thioredoxin 1 and Glutathione S-transferase omega 1 associated with papilloma formation and Enolase 3, Cystatin 6 and Filaggrin associated with TPA-induced proliferation and differentiation. In situ analysis located the papillomas Glutathione S-transferase omega 1 expression to the proliferating areas of the papillomas. Thus we have identified profiles of differential gene expression associated with the tumorigenesis and promotion stages for skin carcinogenesis in the mouse.

Low-Energy Electron Attachment to the Dichlorodifluoromethane (CCl2F2) Molecule

Results from a joint experimental study of electron attachment to dichlorodifluoromethane (CCl2F2) molecules in the gas phase are reported. In a high resolution electron beam experiment involving two versions of the laser photoelectron attachment method, the relative cross section for formation of the dominant anion Cl- wits measured over the energy range 0.001-1.8 eV at the gas temperature T-G = 300 K. It exhibits cusp structure at thresholds for vibrational excitation of the v(3)(a(1)) mode due to interaction with the attachment channels. With reference to the thermal attachment rate coefficient k(T-e;T-G = 300 K) = 2.2(8) x 10(-9) cm(-3) s(-1) (fitted average from several data), a new highly resolved absolute attachment cross section for TG = 300 K was determined. Partial cross sections for formation of the anions Cl-, Cl-2(-), F-, ClF-, and CCl2F- were measured over the range 0-12 eV, using three different electron beam experiments of medium energy resolution. The dependence of the attachment rate coefficient k(T-e;T-G = 300 K) on electron temperature T-e wits calculated over the range 50-15 000 K, based on a newly constructed total cross section for anion formation at T-G = 300 K. R-matrix Calculations for Cl- production have been carried out for comparison with the experimental data. The R-matrix results are in line with the main experimental observations and predict the dependence of the DEA cross section on the initial vibrational level v(3) and on the vibrational temperature. Furthermore, the cross section for I Vibrational excitation of the v(3) mode hits been computed.

Endothelial Nox4 NADPH oxidase enhances vasodilatation and reduces blood pressure in vivo.

OBJECTIVE: Increased reactive oxygen species (ROS) production is involved in the pathophysiology of endothelial dysfunction. NADPH oxidase-4 (Nox4) is a ROS-generating enzyme expressed in the endothelium, levels of which increase in pathological settings. Recent studies indicate that it generates predominantly hydrogen peroxide (H(2)O(2)), but its role in vivo remains unclear. METHODS AND RESULTS: We generated transgenic mice with endothelium-targeted Nox4 overexpression (Tg) to study the in vivo role of Nox4. Tg demonstrated significantly greater acetylcholine- or histamine-induced vasodilatation than wild-type littermates. This resulted from increased H(2)O(2) production and H(2)O(2)-induced hyperpolarization but not altered nitric oxide bioactivity. Tg had lower systemic blood pressure than wild-type littermates, which was normalized by antioxidants. CONCLUSION: Endothelial Nox4 exerts potentially beneficial effects on vasodilator function and blood pressure that are attributable to H(2)O(2) production. These effects contrast markedly with those reported for Nox1 and Nox2, which involve superoxide-mediated inactivation of nitric oxide. Our results suggest that therapeutic strategies to modulate ROS production in vascular disease may need to separately target individual Nox isoforms.

Physicochemical Characterization of Hot Melt Extruded Bicalutamide–Polyvinylpyrrolidone Solid Dispersions

Solid molecular dispersions of bicalutamide (BL) and polyvinylpyrrolidone (PVP) were prepared by hot melt extrusion technology at drug-to-polymer ratios of 1:10, 2:10, and 3:10 (w/w). The solid-state properties of BL, physical mixtures of BL/PVP, and hot melt extrudates were characterized using differential scanning calorimetry (DSC), powder X-ray diffractometry (PXRD), Raman, and Fourier transform infrared (FTIR) spectroscopy. Drug dissolution studies were subsequently conducted on hot melt extruded solid dispersions and physical mixtures. All hot melt extrudates had a single Tg between theTg of amorphous BL and PVP indicating miscibility of BL with PVP and the formation of solid molecular dispersions. PXRD con?rmed the presence of the amorphous form of BL within the extrudates. Conversely, PXRD patterns recorded for physical mixtures showed sharp bands characteristic of crystalline BL, whereas DSC traces had a distinct endotherm at 1968C corresponding to melting of crystalline BL. Further investigations using DSC con?rmed solid-state plasticization of PVP by amorphous BL and hence antiplasticization of amorphous BL by PVP. Experimentally observed Tg values of physical mixtures were shown to be signi?cantly higher than those calculated using the Gordon–Taylor equation suggesting the formation of strong intermolecular interactions between BL and PVP. FTIR and Raman spectroscopy were used to investigate these interactions and strongly suggested the presence of secondary interaction between PVP and BL within the hot melt extrudates. The drug dissolution properties of hot melt extrudates were enhanced signi?cantly in comparison to crystalline BL and physical mixtures. Moreover, the rate and extent of BL release were highly dependent on the amount of PVP present within the extrudate. Storage of the extrudates con?rmed the stability of amorphous BL for up to 12 months at 208C, 40% RH whereas stability was reduced under highly humid conditions (208C, 65% RH). Interestingly, BL recrystallization after storage under these conditions had no effect on the dissolution properties of the extrudates.

On visco-elastic modelling of polyethylene terephthalate behaviour during multiaxial elongations slightly over the glass transition temperature

The mechanical response of Polyethylene Terephthalate (PET) in elongation is strongly dependent on temperature, strain and strain rate. Near the glass transition temperature Tg, the stress-strain curve presents a strain softening effect vs strain rate but a strain hardening effect vs strain under conditions of large deformations. The main goal of this work is to propose a viscoelastic model to predict the PET behaviour when subjected to large deformations and to determine the material properties from the experimental data. To represent the non–linear effects, an elastic part depending on the elastic equivalent strain and a non-Newtonian viscous part depending on both viscous equivalent strain rate and cumulated viscous strain are tested. The model parameters can then be accurately obtained trough a comparison with the experimental uniaxial and biaxial tests. The in?uence of the temperature on the viscous part is also modelled and an evaluation of the adiabatic self heating of the specimen is compared to experimental results.