Computational modelling of bubbles, droplets and particles in metals reduction and refining

A multi-phase framework is typically required for the CFD modelling of metals reduction processes. Such processes typically involve the interaction of liquid metals, a gas (often air) top space, liquid droplets in the top space and injection of both solid particles and gaseous bubbles into the bath. The exchange of mass, momentum and energy between the phases is fundamental to these processes. Multi-phase algorithms are complex and can be unreliable in terms of either or both convergence behaviour or in the extent to which the physics is captured. In this contribution, we discuss these multi-phase flow issues and describe an example of each of the main “single phase” approaches to modelling this class of problems (i.e., Eulerian–Lagrangian and Eulerian–Eulerian). Their utility is illustrated in the context of two problems – one involving the injection of sparging gases into a steel continuous slab caster and the other based on the development of a novel process for aluminium electrolysis. In the steel caster, the coupling of the Lagrangian tracking of the gas phase with the continuum enables the simulation of the transient motion of the metal–flux interface. The model of the electrolysis process employs a novel method for the calculation of slip velocities of oxygen bubbles, resulting from the dissolution of alumina, which allows the efficiency of the process to be predicted.

Heavy metals in the Fal estuary, Cornwall: A study of long term contamination by mining waste and its effects on estuarine organisms. Occasional Publication of the Marine Biological Association 2

The Fal Estuary System in West Cornwall has, over many centuries, received inputs of heavy metals from various mining activities. In this context its most important tributary is the Carnon River. Analyses of organisms from the Fal Estuary have shown that some species contain abnormally high concentrations of Cu, Zn and As, especially those living in Restronguet Creek.

A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air 13C/12C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl2F2) and CFC-113 (C2Cl3F3). Significant, but consistent, isotopic shifts of -27.5 to -25.6 do occur within the system for CFC-11 (CCl3F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (10 L). Representative urban air analyses from Belfast City are also presented which give carbon isotope results similar to published values for 13C/12C analysis of MeCl (-39.1) and CFC-113 (-28.1). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4) and CFC-12 (-37.0).

Biology, ecology, population dynamics and distribution of metals in Sepia officinalis on a typical estuarine coastal lagoon - Ria de Aveiro

The common cuttlefish, Sepia officinalis, is a necto-benthic cephalopod that can live in coastal ecosystems, with high influence of anthropogenic pressures and thus be vulnerable to exposure to various types of contaminants. The cuttlefish is a species of great importance to the local economy of Aveiro, considering the global data of catches of this species in the Ria de Aveiro. However, studies on this species in Ria de Aveiro are scarce, so the present study aims to fill this information gap about the cuttlefish in the Ria de Aveiro. The cuttlefish enters Ria de Aveiro in the spring and summer to reproduce, returning to deeper waters in the winter. In terms of abundance, the eastern and center regions of the lagoon, closer to the sea, showed the highest values of abundance, while the northern and southern regions of the main channel had the lowest abundance. This fact may be related to abiotic factors, as well as depth, salinity and temperature. In the most southern point of the Ria de Aveiro (Areão) no cuttlefish was caught. This site had the lowest values of salinity and depth. The cuttlefish has an allometric the females being heavier than males to mantle lengths greater than 82.4 mm. Males reach sexual maturity first than females. In Ria de Aveiro in a generation of parents was found. The cuttlefish, presents itself as opportunistic predators, consuming a wide variety of prey from different taxa. The diet was similar in different sampling locations observing significant differences for the seasons. S. officinalis was captured at 10 sites in the Ria de Aveiro with different anthropogenic sources of contamination. Thus, levels of metals analyzed were similar at all sampling sites, with the exception of a restricted area, Laranjo, which showed higher values. The cuttlefish has the ability to accumulate metals in your body. The levels of Fe, Zn, Cu, Cd, Pb and Hg found in the digestive gland and mantle reflect a differential accumulation of metals in the tissues. This accumulation is related to the type and function of tissue analyzed and the type of metal analysis (essential and non-essential). The metal concentrations in the digestive gland are higher than in the mantle, with the exception of mercury. This may be due to the high affinity of the mantle for the incorporation of methylmercury (MeHg), the most abundant form of mercury. The accumulation of metals can vary over a lifetime, depending on the metal. The concentrations of Zn, Cd and Hg increases throughout life, while Pb decreases and essential metals such as Fe and Cu remain constant. The data collected suggest that the cuttlefish (Sepia officinalis) can be used as a bioindicator of environmental contamination for some metals.

Modelling Atmospheric Concentrations of Ragweed Pollen From Local and Distant Sources

Pollen grains from the genus ragweed (Ambrosia spp.) are important aeroallergens. In Europe, the largest sources of atmospheric ragweed pollen are the Rhône Valley (France), parts of Northern Italy, the Pannonian Plain and Ukraine. Episodes of Long Distance Transport (LDT) of ragweed pollen from these centres can cover large parts of Europe and are predominantly studied using receptor based models (Smith et al., (2013) and references therein). The clinical impact of allergenic ragweed pollen arriving from distant sources remains unclear (Cecchi et al. 2010). Although a recent study has found the major allergens of ragweed in air samples collected in Poznań, Poland, during episodes of long-distance transport from the Pannonian Plain (Grewling et al. 2013). The source orientated models SILAM, DEHM, COSMO-Art, METRAS and ENVIRO-HIRLAM currently report having the capability of modelling atmospheric concentrations of pollen in Europe. The performance of such source-orientated models is strongly dependent on the quality of the emissions data, which is a focus of current research (e.g. Thibaudon et al. (2014)). The output from these models are important for warning allergy sufferers in areas polluted by ragweed, but could also be used to warn the public of ragweed pollen being transported into areas where the plant is not abundant. Areas outside of the main areas of ragweed infection that contain considerable local populations must, however, also include local scale models. These models can be used to predict local concentrations, even when LDT is not present. This concept of combined LDT and local scale calculations has been shown to be work for air pollutants and is considered usable for urban scale calculations of aeroallergens once urban scale maps of aeroallergen sources have been produced.

Investigating and Predicting Atmospheric Concentrations of Allergenic Fungal Spores (Alternaria, Cladosporium, Didymella and Ganoderma)

Air quality is an increasing concern of the European Union, local authorities, scientists and most of all inhabitants that become more aware of the quality of the surrounding environment. Bioaerosols may be consisted of various elements, and the most important are pollen grains, fungal spores, bacteria, viruses. More than 100 genera of fungal spores have been identified as potential allergens that cause immunological response in susceptible individuals. Alternaria and Cladosporium have been recognised as the most important fungal species responsible for respiratory tract diseases, such as asthma, eczema, rhinitis and chronic sinusitis. While a lot of attention has been given to these fungal species, a limited number of studies can be found on Didymella and Ganoderma, although their allergenic properties were proved clinically. Monitoring of allergenic fungal spore concentration in the air is therefore very important, and in particular at densely populated areas like Worcester, UK. In this thesis a five year spore data set was presented, which was collected using a 7-day volumetric spore trap, analysed with the aid of light microscopy, statistical tests and geographic information system techniques. Although Kruskal-Wallis test detected statistically significant differences between annual concentrations of all examined fungal spore types, specific patterns in their distribution were also found. Alternaria spores were present in the air between mid-May/mid-June until September-October with peak occurring in August. Cladosporium sporulated between mid-May and October, with maximum concentration recorded in July. Didymella spores were seen from June/July up to September, while peaks were found in August. Ganoderma produced spores for 6 months (May-October), and maximum concentration could be found in September. With respect to diurnal fluctuations, Alternaria peaked between 22:00h and 23:00h, Cladosporium 13:00-15:00h, Didymella 04:00-05:00h and 22:00h-23:00h and Ganoderma from 03:00h to 06:00h. Spatial analysis showed that sources of all fungal species were located in England, and there was no evidence for a long distance transport from the continent. The maximum concentration of spores was found several hours delayed in comparison to the approximate time of the spore release from the crops. This was in agreement with diurnal profiles of the spore concentration recorded in Worcester, UK. Spores of Alternaria, Didymella and Ganoderma revealed a regional origin, in contrast to Cladosporium, which sources were situated locally. Hence, the weather conditions registered locally did not exhibit strong statistically significant correlations with fungal spore concentrations. This has had also an impact on the performance of the forecasting models. The best model was obtained for Cladosporium with 66% of the accuracy.

Sub-Lethal effects of heavy metals on perna indica ( Kuriakose & Nair) and donax incarnatus gmelin

The present scientific investigation of the effects of copper, mercury and cadmium has focussed on their effects on two commercially important marine bivalve species, Perna indica (brown mussel) and Donax incarnatus (wedge clam), conspicuous representatives of the tropical intertidal areas. The investigation centred around delineating the cause and effects of heavy metal stress, individually and in combination on these species under laboratory conditions. A clear understanding of the cause and effect can be had only if laboratory experiments are conducted employing sub-lethal concentrations of the above toxicants. Therefore, during the course of the investigation, sub-lethal concentrations of copper, mercury and cadmium were employed to assess the concentration dependent effects on survival, ventilation rate, O:N ratio and tissues. The results obtained are compared with the already available information and partitioned in sections to make a meaningful presentation.The thesis is presented in five chapters comprising INTRODUCTION, ACUTE TOXICITY, VENTILATION RATE, OXYGEN : NITROGEN RATIO and HISTOPATHOLOGY. Each chapter has been divided into various sections such as INTRODUCTION, REVIEW OF LITERATURE, MATERIAL AND METHODS, RESULTS and DISCUSSION

Chemical Evaluation of Selected Organics and Trace Metals in the Mangrove Macroflora Of Cochin

Mangroves are considered to play a significant role in global carbon cycling. Themangrove forests would fix CO2 by photosynthesis into mangrove lumber and thus decrease the possibility of a catastrophic series of events - global warming by atmospheric CO2, melting of the polar ice caps, and inundation of the great coastal cities of the world. The leaf litter and roots are the main contributors to mangrove sediments, though algal production and allochthonous detritus can also be trapped (Kristensen et al, 2008) by mangroves due to their high organic matter content and reducing nature are excellent metal retainers. Environmental pollution due to metals is of major concern. This is due to the basic fact that metals are not biodegradable or perishable the way most organic pollutants are. While most organic toxicants can be destroyed by combustion and converted into compounds such as C0, C02, SOX, NOX, metals can't be destroyed. At the most the valance and physical form of metals may change. Concentration of metals present naturally in air, water and soil is very low. Metals released into the environment through anthropogenic activities such as burning of fossils fuels, discharge of industrial effluents, mining, dumping of sewage etc leads to the development of higher than tolerable or toxic levels of metals in the environment leading to metal pollution. Of course, a large number of heavy metals such as Fe, Mn, Cu, Ni, Zn, Co, Cr, Mo, and V are essential to plants and animals and deficiency of these metals may lead to diseases, but at higher levels, it would lead to metal toxicity. Almost all industrial processes and urban activities involve release of at least trace quantities of half a dozen metals in different forms. Heavy metal pollution in the environment can remain dormant for a long time and surface with a vengeance. Once an area gets toxified with metals, it is almost impossible to detoxify it. The symptoms of metal toxicity are often quite similar to the symptoms of other common diseases such as respiratory problems, digestive disorders, skin diseases, hypertension, diabetes, jaundice etc making it all the more difficult to diagnose metal poisoning. For example the Minamata disease caused by mercury pollution in addition to affecting the nervous system can disturb liver function and cause diabetes and hypertension. The damage caused by heavy metals does not end up with the affected person. The harmful effects can be transferred to the person's progenies. Ironically heavy metal pollution is a direct offshoot of our increasing ability to mass produce metals and use them in all spheres of existence. Along with conventional physico- chemical methods, biosystem approachment is also being constantly used for combating metal pollution

Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

Spatio-temporal variations of ozone and nitrogen dioxide concentrations under urban trees and in a nearby open area

The evergreen Quercus ilex L. is one of the most common trees in Italian urban environments and is considered effective in the uptake of particulate and gaseous atmospheric pollutants. However, the few available estimates on O3 and NO2 removal by urban Q. ilex originate from model-based studies (which indicate NO2/O3 removal capacity of Q. ilex) and not from direct measurements of air pollutant concentrations. Thus, in the urban area of Siena (central Italy) we began long-term monitoring of O3/NO2 concentrations using passive samplers at a distance of 1, 5, 10 m from a busy road, under the canopies of Q. ilex and in a nearby open-field. Measurements performed in the period June 2011-October 2013 showed always a greater decrease of NO2 concentrations under the Q. ilex canopy than in the open-field transect. Conversely, a decrease of average O3 concentrations under the tree canopy was found only in autumn after the typical Mediterranean post-summer rainfalls. Our results indicate that interactions between O3/NO2 concentrations and trees in Mediterranean urban ecosystems are affected by temporal variations in climatic conditions. We argue therefore that the direct measurement of atmospheric pollutant concentrations should be chosen to describe local changes of aerial pollution.

Heathland restoration on former agricultural land: effects of artificial acidification on the availability and uptake of toxic metal cations

Lowland heath is an internationally important habitat type that has greatly declined in abundance throughout Western Europe. In recent years this has led to a growing interest in the restoration of heathland on agricultural land. This generally requires the use of chemical treatments to return soil chemical conditions to those appropriate for the support of heathland ecosystems. However, the potential for negative impacts on the environment due to the potential of these treatments to increase the availability of trace metals via raised soil acidity requires investigation. A large-scale field study investigated the effect of two chemical treatments used in heathland restoration, elemental sulphur and ferrous sulphate, on soil acidity and whether it is possible to predict the effect of the treatments on availability of two potentially toxic cations (Al and Cd) in the soil along with their subsequent accumulation in the shoots of the grass Agrostis capillaris. Results showed that both treatments decreased soil pH, but that only elemental sulphur produced a pH similar to heathland soil. The availability of Al, measured by extraction with 1 M ammonium nitrate, could not be predicted by soil pH, depth in the soil and total Al concentration in the soil. By contrast, availability of Cd could be predicted from these three variables. Concentrations of both Al and Cd in the shoots of A. capillaris showed no significant relationship with the extractable concentration in the soil. Results are discussed in light of the possible environmental impacts of the chemical restoration techniques.

The impact of European legislative and technology measures to reduce air pollutants on air quality, human health and climate

European air quality legislation has reduced emissions of air pollutants across Europe since the 1970s, affecting air quality, human health and regional climate. We used a coupled composition-climate model to simulate the impacts of European air quality legislation and technology measures implemented between 1970 and 2010. We contrast simulations using two emission scenarios; one with actual emissions in 2010 and the other with emissions that would have occurred in 2010 in the absence of technological improvements and end-of-pipe treatment measures in the energy, industrial and road transport sectors. European emissions of sulphur dioxide, black carbon (BC) and organic carbon in 2010 are 53%, 59% and 32% lower respectively compared to emissions that would have occurred in 2010 in the absence of legislative and technology measures. These emission reductions decreased simulated European annual mean concentrations of fine particulate matter(PM2.5) by 35%, sulphate by 44%, BC by 56% and particulate organic matter by 23%. The reduction in PM2.5 concentrations is calculated to have prevented 80 000 (37 000–116 000, at 95% confidence intervals) premature deaths annually across the European Union, resulting in a perceived financial benefit to society of US$232 billion annually (1.4% of 2010 EU GDP). The reduction in aerosol concentrations due to legislative and technology measures caused a positive change in the aerosol radiative effect at the top of atmosphere, reduced atmospheric absorption and also increased the amount of solar radiation incident at the surface over Europe. We used an energy budget approximation to estimate that these changes in the radiative balance have increased European annual mean surface temperatures and precipitation by 0.45 ± 0.11 °C and by 13 ± 0.8 mm yr−1 respectively. Our results show that the implementation of European legislation and technological improvements to reduce the emission of air pollutants has improved air quality and human health over Europe, as well as having an unintended impact on the regional radiative balance and climate.

Bioaccumulation of chlorinated pesticides and PCBs in the tropical freshwater fish Hoplias malabaricus: Histopathological, physiological, and immunological findings

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Experimental measurements of the NOx and CO concentrations operating in oscillatory and non-oscillatory burning conditions

The effects of combustion driven acoustic oscillations in carbon monoxide and nitrogen oxides emission rates of a combustor operated with liquefied petroleum gas (LPG) were investigated. Because the fuel does not contain nitrogen, tests were also conducted with ammonia injected in the fuel, in order to study the formation of fuel NOx. The main conclusions were: (a) the pulsating combustion process is more efficient than the non-pulsating one and (b) the pulsating combustion process generates higher rates of NOx, with and without ammonia injection, as shown by CO and NO concentrations as function of the O-2 concentration. An increase in the LPG flow rate, keeping constant the air to fuel ratio, increased the acoustic pressure amplitude and the frequency of oscillation. The injection of ammonia had no influence on either pressure amplitude or frequency. (c) 2005 Elsevier Ltd. All rights reserved.