Gas chromatographic electron capture negative ionization mass spectrometric (GC/ECNI/MS) determination of unique fluorinated compounds in the sediments of Lake Ontario and the effect of high-boiling alcohols (as injection solvents) on chromatographic behaviour of polycyclic aromatic hydrocarbons in gas chromatography

Part I - Fluorinated Compounds A method has been developed for the extraction, concentration, and determination of two unique fluorinated compounds from the sediments of Lake Ontario. These compounds originated from a common industrial landfill, and have been carried to Lake Ontario by the Niagara River. Sediment samples from the Mississauga basin of Lake Ontario have been evaluated for these compounds and a depositional trend was established. The sediments were extracted by accelerated solvent extraction (ASE) and then underwent clean-up, fractionation, solvent exchange, and were concentrated by reduction under nitrogen gas. The concentrated extracts were analyzed by gas chromatography - electron capture negative ionization - mass spectrometry. The depositional profile determined here is reflective of the operation of the landfill and shows that these compounds are still found at concentrations well above background levels. These increased levels have been attributed to physical disturbances of previously deposited contaminated sediments, and probable continued leaching from the dumpsite. Part II - Polycyclic Aromatic Hydrocarbons Gas chromatography/mass spectrometry is the most common method for the determination of polycyclic aromatic hydrocarbons (PAHs) from various matrices. Mass discrimination of high-boiling compounds in gas chromatographic methods is well known. The use of high-boiling injection solvents shows substantial increase in the response of late-eluting peaks. These solvents have an increased efficiently in the transfer of solutes from the injector to the analytical column. The effect of I-butanol, I-pentanol, cyclopentanol, I-hexanol, toluene and n-octane, as injection solvents, was studied. Higher-boiling solvents yield increased response for all PAHs. I -Hexanol is the best solvent, in terms of P AH response, but in this solvent P AHs were more susceptible to chromatographic problems such as peak splitting and tailing. Toluene was found to be the most forgiving solvent in terms of peak symmetry and response. It offered the smallest discrepancies in response, and symmetry over a wide range of initial column temperatures.

The EU budget becomes politically more explosive. CEPS Commentary, 3 December 2012

H. Onno Ruding describes the negotiations on the EU budget, which will resume in 2013 following their collapse in late November, as “more awkward than usual”. In this new CEPS Commentary, he advises EU leaders to make the instrument more forward-looking in promoting economic growth in Europe and less focused on maintaining legacy entitlements of past years. In his view, this means more spending on research, innovation, education and infrastructure and also requires further reductions in the still-dominant agricultural subsidies as well as regional and structural funds.

A stress-controlled mechanism for the intensity of very large magnitude explosive eruptions

Large magnitude explosive eruptions are the result of the rapid and large-scale transport of silicic magma stored in the Earth's crust, but the mechanics of erupting teratonnes of silicic magma remain poorly understood. Here, we demonstrate that the combined effect of local crustal extension and magma chamber overpressure can sustain linear dyke-fed explosive eruptions with mass fluxes in excess of 10^10 kg/s from shallow-seated (4–6 km depth) chambers during moderate extensional stresses. Early eruption column collapse is facilitated with eruption duration of the order of few days with an intensity of at least one order of magnitude greater than the largest eruptions in the 20th century. The conditions explored in this study are one way in which high mass eruption rates can be achieved to feed large explosive eruptions. Our results corroborate geological and volcanological evidences from volcano-tectonic complexes such as the Sierra Madre Occidental (Mexico) and the Taupo Volcanic Zone (New Zealand).

Rossby wave-breaking analysis of explosive cyclones in the Euro-Atlantic sector

The two-way relationship between Rossby Wave-Breaking (RWB) and intensification of extra tropical cyclones is analysed over the Euro-Atlantic sector. In particular, the timing, intensity and location of cyclone development are related to RWB occurrences. For this purpose, two potential-temperature based indices are used to detect and classify anticyclonic and cyclonic RWB episodes from ERA-40 Re-Analysis data. Results show that explosive cyclogenesis over the North Atlantic (NA) is fostered by enhanced occurrence of RWB on days prior to the cyclone’s maximum intensification. Under such conditions, the eddy-driven jet stream is accelerated over the NA, thus enhancing conditions for cyclogenesis. For explosive cyclogenesis over the eastern NA, enhanced cyclonic RWB over eastern Greenland and anticyclonic RWB over the sub-tropical NA are observed. Typically only one of these is present in any given case, with the RWB over eastern Greenland being more frequent than its southern counterpart. This leads to an intensification of the jet over the eastern NA and enhanced probability of windstorms reaching Western Europe. Explosive cyclones evolving under simultaneous RWB on both sides of the jet feature a higher mean intensity and deepening rates than cyclones preceded by a single RWB event. Explosive developments over the western NA are typically linked to a single area of enhanced cyclonic RWB over western Greenland. Here, the eddy-driven jet is accelerated over the western NA. Enhanced occurrence of cyclonic RWB over southern Greenland and anticyclonic RWB over Europe is also observed after explosive cyclogenesis, potentially leading to the onset of Scandinavian Blocking. However, only very intense developments have a considerable influence on the large-scale atmospheric flow. Non-explosive cyclones depict no sign of enhanced RWB over the whole NA area. We conclude that the links between RWB and cyclogenesis over the Euro-Atlantic sector are sensitive to the cyclone’s maximum intensity, deepening rate and location.

Diagnosing the influence of diabatic processes on the explosive deepening of extratropical cyclones

A novel version of the classical surface pressure tendency equation (PTE) is applied to ERA-Interim reanalysis data to quantitatively assess the contribution of diabatic processes to the deepening of extratropical cyclones relative to effects of temperature advection and vertical motions. The five cyclone cases selected, Lothar and Martin in December 1999, Kyrill in January 2007, Klaus in January 2009, and Xynthia in February 2010, all showed explosive deepening and brought considerable damage to parts of Europe. For Xynthia, Klaus and Lothar diabatic processes contribute more to the observed surface pressure fall than horizontal temperature advection during their respective explosive deepening phases, while Kyrill and Martin appear to be more baroclinically driven storms. The powerful new diagnostic tool presented here can easily be applied to large numbers of cyclones and will help to better understand the role of diabatic processes in future changes in extratropical storminess.

Explosive development of winter storm Xynthia over the subtropical North Atlantic Ocean

In winter of 2009–2010 south-western Europe was hit by several destructive windstorms. The most important was Xynthia (26–28 February 2010), which caused 64 reported casualties and was classified as the 2nd most expensive natural hazard event for 2010 in terms of economic losses. In this work we assess the synoptic evolution, dynamical characteristics and the main impacts of storm Xynthia, whose genesis, development and path were very uncommon. Wind speed gusts observed at more than 500 stations across Europe are evaluated as well as the wind gust field obtained with a regional climate model simulation for the entire North Atlantic and European area. Storm Xynthia was first identified on 25 February around 30° N, 50° W over the subtropical North Atlantic Ocean. Its genesis occurred on a region characterized by warm and moist air under the influence of a strong upper level wave embedded in the westerlies. Xynthia followed an unusual SW–NE path towards Iberia, France and central Europe. The role of moist air masses on the explosive development of Xynthia is analysed by considering the evaporative sources. A lagrangian model is used to identify the moisture sources, sinks and moisture transport associated with the cyclone during its development phase. The main supply of moisture is located over an elongated region of the subtropical North Atlantic Ocean with anomalously high SST, confirming that the explosive development of storm Xynthia had a significant contribution from the subtropics.

The role of anomalous SST and surface fluxes over the Southeastern North Atlantic in the explosive development of windstorm Xynthia

In late February 2010 the extraordinary windstorm Xynthia crossed over Southwestern and Central Europe and caused severe damage, affecting particularly the Spanish and French Atlantic coasts. The storm was embedded in uncommon large-scale atmospheric and boundary conditions prior to and during its development, namely enhanced sea surface temperatures (SST) within the low-level entrainment zone of air masses, an unusual southerly position of the polar jet stream, and a remarkable split jet structure in the upper troposphere. To analyse the processes that led to the rapid intensification of this exceptional storm originating close to the subtropics (30°N), the sensitivity of the cyclone intensification to latent heat release is determined using the regional climate model COSMO-CLM forced with ERA-Interim data. A control simulation with observed SST shows that moist and warm air masses originating from the subtropical North Atlantic were involved in the cyclogenesis process and led to the formation of a vertical tower with high values of potential vorticity (PV). Sensitivity studies with reduced SST or increased laminar boundary roughness for heat led to reduced surface latent heat fluxes. This induced both a weaker and partly retarded development of the cyclone and a weakening of the PV-tower together with reduced diabatic heating rates, particularly at lower and mid levels. We infer that diabatic processes played a crucial role during the phase of rapid deepening of Xynthia and thus to its intensity over the Southeastern North Atlantic. We suggest that windstorms like Xynthia may occur more frequently under future climate conditions due to the warming SSTs and potentially enhanced latent heat release, thus increasing the windstorm risk for Southwestern Europe.

Fireballs, flares, and flickering: A semianalytic, LTE, explosive model from accretion disks to supernovae

We derive simple analytic expressions for the continuum light curves and spectra of flaring and flickering events that occur over a wide range of astrophysical systems. We compare these results to data taken from the cataclysmic variable SS Cygni and also from SN 1987A, deriving physical parameters for the material involved. Fits to the data indicate a nearly time-independent photospheric temperature arising from the strong temperature dependence of opacity when hydrogen is partially ionized.

On the relation between explosive cyclones affecting Europe and the North Atlantic oscillation

Intense winter cyclones often lead to hazardous weather over Europe. Previous studies have pointed to a link between the North Atlantic Oscillation (NAO) and strong European windstorms. However, the robustness of this relation for cyclones of varying intensities remains largely unexplored. In this paper, the bi-directional relation between the NAO and cyclones impacting Europe is analyzed for the period 1950–2010 focusing on the sensitivity to storm intensity. Evidence is given that explosive (EC) and non-explosive cyclones (NoEC) predominantly develop under different large-scale circulation conditions over the North Atlantic. Whereas NoEC evolve more frequently under negative and neutral NAO phases, the number of EC is larger under a positive NAO phase, typically characterized by an intensified jet toward Western Europe. Important differences are also found on the dynamics of NAO evolution after peak intensity for both cyclone populations.

Abrupt transitions in the NAO control of explosive North Atlantic cyclone development

Explosive cyclones are intense extra-tropical low pressure systems featuring large deepening rates. In the Euro-Atlantic sector, they are a major source of life-threatening weather impacts due to their associated strong wind gusts, heavy precipitation and storm surges. The wintertime variability of the North Atlantic cyclonic activity is primarily modulated by the North Atlantic Oscillation (NAO). In this study, we investigate the interannual and multi-decadal variability of explosive North Atlantic cyclones using track density data from two reanalysis datasets (NCEP and ERA-40) and a control simulation of an atmosphere/ocean coupled General Circulation Model (GCM—ECHAM5/MPIOM1). The leading interannual and multi-decadal modes of variability of explosive cyclone track density are characterized by a strengthening/weakening pattern between Newfoundland and Iceland, which is mainly modulated by the NAO at both timescales. However, the NAO control of interannual cyclone variability is not stationary in time and abruptly fluctuates during periods of 20–25 years long both in NCEP and ECHAM5/MPIOM1. These transitions are accompanied by structural changes in the leading mode of explosive cyclone variability, and by decreased/enhanced baroclinicity over the sub-polar/sub-tropical North Atlantic. The influence of the ocean is apparently important for both the occurrence and persistence of such anomalous periods. In the GCM, the Atlantic Meridional Overturning Circulation appears to influence the large-scale baroclinicity and explosive cyclone development over the North Atlantic. These results permit a better understanding of explosive cyclogenesis variability at different climatic timescales and might help to improve predictions of these hazardous events.

The bubbles or the boiling pot? An ecosystemic approach to culture, environment and quality of life

For the diagnosis and prognosis of the problems of quality of life, a multidisciplinary ecosystemic approach encompasses four dimensions of being-in-the-world, as donors and recipients: intimate, interactive, social and biophysical. Social, cultural and environmental vulnerabilities are understood and dealt with, in different circumstances of space and time, as the conjugated effect of all dimensions of being-in-the-world, as they induce the events (deficits and assets), cope with consequences (desired or undesired) and contribute for change. Instead of fragmented and reduced representations of reality, diagnosis and prognosis of cultural, educational, environmental and health problems considers the connections (assets) and ruptures (deficits) between the different dimensions, providing a planning model to develop and evaluate research, teaching programmes, public policies and field projects. The methodology is participatory, experiential and reflexive; heuristic-hermeneutic processes unveil cultural and epistemic paradigms that orient subject-object relationships; giving people the opportunity to reflect on their own realities, engage in new experiences and find new ways to live better in a better world. The proposal is a creative model for thought and practice, providing many opportunities for discussion, debate and development of holistic projects integrating different scientific domains (social sciences, psychology, education, philosophy, etc.).

Influence of Fluid Concentration on the Elevation of Boiling Point of Blackberry Juice

The rise in boiling point of blackberry juice was experimentally measured at soluble solids concentrations in the range of 9.4 to 58.4Brix and pressures between 4.9 103 and 9.0 104 Pa (abs.). Different approaches to representing experimental data, including the Duhring`s rule, a model similar to Antoine equation and other empirical models proposed in the literature were tested. In the range of 9.4 to 33.6Brix, the rise in boiling point was nearly independent of pressure, varying only with juice concentration. Considerable deviations of this behavior began to occur at concentrations higher than 39.1Brix. Experimental data could be best predicted by adjusting an empirical model, which consists of a single equation that takes into account the dependence of rise in boiling point on pressure and concentration.

Improved Prediction of Hydrocarbon Flash Points from Boiling Point Data

Flash points (T(FP)) of hydrocarbons are calculated from their flash point numbers, N(FP), with the relationship T(FP) (K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 In turn, the N(FP) values can be predicted from experimental boiling point numbers (Y(BP)) and molecular structure with the equation N(FP) = 0.987 Y(BP) + 0.176D + 0.687T + 0.712B - 0.176 where D is the number of olefinic double bonds in the structure, T is the number of triple bonds, and B is the number of aromatic rings. For a data set consisting of 300 diverse hydrocarbons, the average absolute deviation between the literature and predicted flash points was 2.9 K.

Study of Monoethanolamine Nitrate Content Reduction in Explosive Slurries

The reduction of the fuel content of a monoethanolamine nitrate (MEAN) fueled explosive slurry was investigated. The work was performed in three phases. The first one involved the MEAN content reduction in a reference slurry from its initial value of 36 down to 24% by weight, the balance being filled with ammonium nitrate, the least expensive item in the slurry composition. This proved to be successful, leading to an overall cost reduction of 17%, while keeping the overall performance quite satisfactory. The second phase consisted in trying to bring the MEAN content down from 24 to 17%. Although this led to further cost reduction, the formulations, obtained by substituting part of the MEAN content by ammonium nitrate/fuel oil (ANFO), produced unsatisfactory results regarding ignition and densities. In the third phase, the Design of Experiments Technique was used to find formulations displaying not only lower cost, but also acceptable overall performance. This led to a raw material cost reduction ranging from 23 to 26% relative to the initial reference slurry formulation.

Molecular identification and thermoresistance to boiling of Nocardia farcinica and Nocardia cyriacigeorgica from bovine bulk tank milk

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)